CN103228713A - Polylactic acid film or sheet - Google Patents

Abstract

A polylactic acid film or sheet is a resin film or a sheet containing polylactic acid (A), wherein the melting endothermic value (delta HC') in a crystallization section at the time of film-forming, which is called for by formula (1) delta HC'= delta Hm- delta Hc (1) (In the formula, delta HC is the exothermic value (J/g) accompanied with crystallization in the heating process of the film or sheet after film-forming, and is measured using a DSC; delta Hm is the endothermic value (J/g) accompanied with the melting thereafter.), is 10J/g or more, and a tearing strength in a flow direction (MD direction) and a width direction (TD direction) both are 2.5N/mm or more. This polylactic acid film or sheet does not melt or deform even at temperatures exceeding 100 DEG C, and furthermore, during production and machining of the film or sheet, no breakage or tearing, when the film or the sheet is rolled into a roll or the like, happans.

Description

Poly lactic acid series film or sheet

Technical field

The present invention relates to poly lactic acid series film or sheet, more specifically, relate to excellent heat resistance and during fabrication, add and can not produce fracture, rimose poly lactic acid series film or sheet man-hour.

In addition, the present invention relates to barrier film, more specifically, relate to excellent heat resistance and during fabrication, add and can not produce fracture, rimose poly lactic acid series film or sheet barrier film (release liner) man-hour as base material.This barrier film can be used for protecting the tackiness agent aspect of self adhesive tape, adhesive sheet, label etc.

And then, the present invention relates to self adhesive tape or sheet, more specifically, relate to excellent heat resistance and during fabrication, add and can not produce fracture, rimose poly lactic acid series film or sheet self adhesive tape or sheet man-hour as base material.

Have again, the present invention relates to protective film (comprising sheet), more specifically, relate to excellent heat resistance and during fabrication, add and can not produce fracture, rimose poly lactic acid series film or sheet protective film man-hour as base material.This protective film can be at the protective film on the surface that is used to protect the automotive wheel circle; Be used for protecting the protective film on the surface of optics such as the Polarizer that uses at liquid-crystal display etc., wavelength plate, polarizer, reflector plate or electronic unit; Be used for protecting use in the protective film on the surface of metal level that the electromagnetic shielding material of plasm display panel, CRT etc. uses or metal oxide layer etc.Protective film can be peeled off removal in the unwanted stage.

Background technology

Poly(lactic acid) is the biomass polymkeric substance from plant, instead from the resin of the polymkeric substance of oil and receive publicity.Yet the crystallization speed of poly(lactic acid) is slow, hardly can crystallization by common one-tenth membrane means.Therefore, the film that is formed by the resin combination that contains poly(lactic acid) exists when the second-order transition temperature of poly(lactic acid) is more than 60 ℃ and produces thermal distortion, can't keep the such problem of film shape.Therefore, in order to improve the thermotolerance of polylactic acid based resin film, Several Methods had been proposed in the past.

For example, known have after will containing the resin combination filming of poly(lactic acid) by extrusion by melting, makes its stretching and oriented crystallineization by biaxial stretch-formed, improves the stable on heating method of polylactic acid based resin film thus.Yet, in the method, because the internal residual stresses when exist stretching, uprise the thermal contraction meeting very big such shortcoming that becomes if therefore have use temperature.Therefore, the as many as of the temperature that in fact can use is about 100 ℃.

In Japanese kokai publication hei 11-116788 communique (patent documentation 1), proposed to improve stable on heating method by blend materials with high melting point in poly(lactic acid).Yet the component ratio (biomass degree) from plant can reduce in the method.

In TOHKEMY 2010-106272 communique (patent documentation 2), the manufacture method of a kind of polylactic acid based resin film or sheet is disclosed, it is characterized in that its temperature range in the crystallized temperature from the temperature-fall period of this resin combination (Tc)+15 ℃ melting temperature (Tm) (Tm)-5 to the temperature-rise period of this resin combination ℃ is carried out the fusion film forming to the resin combination that contains poly(lactic acid); Perhaps after will containing the resin combination fusion film forming of poly(lactic acid), promote the crystalline operation under the temperature of the crystallized temperature (Tc) ± 10 of experience in the temperature-fall period of this resin combination ℃, then cooling curing.Yet,, during fabrication, add man-hour, when being wound into the roller shape etc., might produce fracture, cracking at film or sheet place though polylactic acid based resin film that obtains like this or sheet thermotolerance improve.Therefore, when this film or sheet are used as base materials such as barrier film (release liner), self adhesive tape, protective films, when the manufacturing of barrier film etc., the man-hour of adding, locate to produce sometimes fracture, cracking at barrier film etc.

The prior art document

Patent documentation

Patent documentation 1: Japanese kokai publication hei 11-116788 communique

Patent documentation 2: TOHKEMY 2010-106272 communique

Summary of the invention

The problem that invention will solve

Therefore, the object of the present invention is to provide a kind of polylactic acid based resin film or sheet, even it is surpassing under 100 ℃ the high temperature, film or sheet can not fuse yet, be out of shape, and when the manufacturing of film or sheet, the man-hour of adding, can not produce fracture, cracking when film or sheet are wound into the roller shape etc.

In addition, another object of the present invention is to provide a kind of with poly lactic acid series film or sheet barrier film as base material, even this poly lactic acid series film or sheet are surpassing under 100 ℃ the high temperature, base material can not fuse yet, be out of shape, and when the manufacturing of barrier film, the man-hour of adding, can not produce fracture, cracking when being wound into the roller shape etc.

And then, another object of the present invention is to provide a kind of with poly lactic acid series film or sheet self adhesive tape or sheet as base material, even this poly lactic acid series film or sheet are surpassing under 100 ℃ the high temperature, base material can not fuse yet, be out of shape, and when the manufacturing of self adhesive tape or sheet, the man-hour of adding, can not produce fracture, cracking when being wound into the roller shape etc.

Have again; another object of the present invention is to provide a kind of with poly lactic acid series film or sheet protective film as base material; even this poly lactic acid series film or sheet are surpassing under 100 ℃ the high temperature; base material can not fuse yet, be out of shape; and when the manufacturing of protective film, the man-hour of adding, can not produce fracture, cracking when being wound into the roller shape etc.

The scheme that is used to deal with problems

The inventor etc. further investigate in order to reach above-mentioned purpose, found that, the fusion of crystallization portion caloric receptivity is located at more than the particular value by with polylactic acid based resin film or sheet film forming the time, and tear strength is located at more than the certain value, can address the above problem, thereby finish the present invention.

That is, the present invention is a kind of poly lactic acid series film or sheet, it is characterized in that, it is for containing the resin film or the sheet of poly(lactic acid) (A), and the fusion caloric receptivity Δ Hc ' of crystallization portion is more than the 10J/g during its film forming of trying to achieve by following formula (1),

ΔHc′＝ΔHm-ΔHc （1）

[in the formula, Δ Hc is accompanied by the thermal discharge (J/g) of crystallization for film that measure by DSC, after the film forming or sheet at temperature-rise period, and Δ Hm is the caloric receptivity (J/g) that is accompanied by fusion thereafter]

And tear strength (according to JIS P8116 paper-tear strength test method-Elmendorf type tear tester method) is more than the 2.5N/mm at travel direction (MD direction), width (TD direction).

Aforementioned poly lactic acid series film or sheet can further contain 0.5～15 weight part fluorine based polymer (B) with respect to 100 weight part poly(lactic acid) (A).Fluorine based polymer (B) can be the tetrafluoroethylene based polymer.

Aforementioned poly lactic acid series film or sheet can further contain 0.1～15 weight part crystallization promoter (C) with respect to 100 weight part poly(lactic acid) (A).

Aforementioned poly lactic acid series film or sheet can further contain 0.1～10 weight part acidic functionality modified olefin based polymer (D) with respect to 100 weight part poly(lactic acid) (A), and the acid value of described acidic functionality modified olefin based polymer (D) is that 10～70mgKOH/g, weight-average molecular weight are 10000～80000.

Aforementioned poly lactic acid series film or sheet can be for by being melt into film or the sheet that embrane method for example obtains by the rolling process film forming.

In addition, the invention provides a kind of barrier film, it is characterized in that, it is for there being the barrier film of stripper processing layer at least one mask of barrier film base material, and this barrier film base material is made of aforesaid poly lactic acid series film or sheet.

And then, the invention provides a kind of self adhesive tape or sheet, it is characterized in that it is for having the self adhesive tape or the sheet of binder layer at least one mask of base material, this base material is made of aforesaid poly lactic acid series film or sheet.

Have, the invention provides a kind of protective film, it is characterized in that, it is for there being the protective film of releasable binder layer at least one mask of base material, and this base material is made of aforesaid poly lactic acid series film or sheet.

In this manual, except technique scheme, also following poly lactic acid series film or sheet, barrier film, self adhesive tape or sheet and the related technical scheme of protective film are described.

[1-1] a kind of poly lactic acid series film or sheet, it is characterized in that, it is for containing the resin film or the sheet of poly(lactic acid) (A), with respect to this 100 weight part poly(lactic acid) (A), contain 1～20 mass parts polyglycerol fatty acid ester and/or Polyglycerine condensation hydroxy fatty acid (F) in total amount, and during the film forming of trying to achieve by following formula (1) the fusion caloric receptivity Δ Hc ' of crystallization portion for more than the 10J/g.

ΔHc′＝ΔHm-ΔHc （1）

[in the formula, Δ Hc is accompanied by the thermal discharge (J/g) of crystallization for film that measure by DSC, after the film forming or sheet at temperature-rise period, and Δ Hm is the caloric receptivity (J/g) that is accompanied by fusion thereafter]

[1-2] according to aforementioned [1-1] described poly lactic acid series film or sheet, it further contains 0.5～15 weight part fluorine based polymer (B) with respect to 100 weight part poly(lactic acid) (A).

[1-3] according to aforementioned [1-2] described poly lactic acid series film or sheet, wherein, fluorine based polymer (B) is the tetrafluoroethylene based polymer.

[1-4] according to each described poly lactic acid series film or sheet among aforementioned [1-1]～[1-3], it further contains 0.1～15 weight part crystallization promoter (C) with respect to 100 weight part poly(lactic acid) (A).

[1-5] is according to each described poly lactic acid series film or sheet among aforementioned [1-1]～[1-4], it further contains 0.1～10 weight part acidic functionality modified olefin based polymer (D) with respect to 100 weight part poly(lactic acid) (A), and the acid value of described acidic functionality modified olefin based polymer (D) is that 10～70mgKOH/g, weight-average molecular weight are 10000～80000.

[1-6] according to each described poly lactic acid series film or sheet among aforementioned [1-1]～[1-5], and it is for by being melt into film or the sheet that the embrane method film forming obtains.

[1-7] according to aforementioned [1-6] described poly lactic acid series film or sheet, wherein, being melt into embrane method is rolling process.

[1-8] a kind of barrier film is characterized in that, it is for there being the barrier film of stripper processing layer at least one mask of barrier film base material, and this barrier film base material is to be made of each described poly lactic acid series film among aforementioned [1-1]～[1-7] or sheet.

[1-9] a kind of self adhesive tape or sheet is characterized in that, it is for having the self adhesive tape or the sheet of binder layer at least one mask of base material, and this base material is to be made of each described poly lactic acid series film among aforementioned [1-1]～[1-7] or sheet.

[1-10] a kind of protective film is characterized in that, it is for there being the protective film of releasable binder layer at least one mask of base material, and this base material is made of each described poly lactic acid series film or sheet among aforementioned [1-1]～[1-7].

[2-1] a kind of poly lactic acid series film or sheet, it is characterized in that, it is for containing the resin film or the sheet of poly(lactic acid) (A), it is with respect to this poly(lactic acid) of 100 weight parts (A), contain 1～20 weight part has the grafting layer in the outside of granular rubber nucleocapsid structure polymkeric substance (G), and during its film forming of trying to achieve by following formula (1) the fusion caloric receptivity Δ Hc ' of crystallization portion for more than the 10J/g.

ΔHc′＝ΔHm-ΔHc （1）

[in the formula, Δ Hc is accompanied by the thermal discharge (J/g) of crystallization for film that measure by DSC, after the film forming or sheet at temperature-rise period, and Δ Hm is the caloric receptivity (J/g) that is accompanied by fusion thereafter]

[2-2] according to aforementioned [2-1] described poly lactic acid series film or sheet, it further contains 0.5～15 weight part fluorine based polymer (B) with respect to 100 weight part poly(lactic acid) (A).

[2-3] according to aforementioned [2-2] described poly lactic acid series film or sheet, wherein, fluorine based polymer (B) is the tetrafluoroethylene based polymer.

[2-4] according to each described poly lactic acid series film or sheet among aforementioned [2-1]～[2-3], it further contains 0.1～15 weight part crystallization promoter (C) with respect to 100 weight part poly(lactic acid) (A).

[2-5] is according to each described poly lactic acid series film or sheet among aforementioned [2-1]～[2-4], it further contains 0.1～10 weight part acidic functionality modified olefin based polymer (D) with respect to 100 weight part poly(lactic acid) (A), and the acid value of described acidic functionality modified olefin based polymer (D) is that 10～70mgKOH/g, weight-average molecular weight are 10000～80000.

[2-6] according to each described poly lactic acid series film or sheet among aforementioned [2-1]～[2-5], and it is for by being melt into film or the sheet that the embrane method film forming obtains.

[2-7] according to aforementioned [2-6] described poly lactic acid series film or sheet, wherein, being melt into embrane method is rolling process.

[2-8] a kind of barrier film is characterized in that, it is for there being the barrier film of stripper processing layer at least one mask of barrier film base material, and this barrier film base material is made of each described poly lactic acid series film or sheet among aforementioned [2-1]～[2-7].

[2-9] a kind of self adhesive tape or sheet is characterized in that, it is for having the self adhesive tape or the sheet of binder layer at least one mask of base material, and this base material is to be made of each described poly lactic acid series film among aforementioned [2-1]～[2-7] or sheet.

[2-10] a kind of protective film is characterized in that, it is for there being the protective film of releasable binder layer at least one mask of base material, and this base material is to be made of each described poly lactic acid series film among aforementioned [2-1]～[2-7] or sheet.

[3-1] a kind of poly lactic acid series film or sheet, it is characterized in that, it is for containing the resin film or the sheet of poly(lactic acid) (A), it is with respect to this poly(lactic acid) of 100 weight parts (A), contain the soft fatty family polyester of 5～30 weight parts (H), and during its film forming of trying to achieve by following formula (1) the fusion caloric receptivity Δ Hc ' of crystallization portion for more than the 10J/g.

ΔHc′＝ΔHm-ΔHc （1）

[in the formula, Δ Hc is accompanied by the thermal discharge (J/g) of crystallization for film that measure by DSC, after the film forming or sheet at temperature-rise period, and Δ Hm is the caloric receptivity (J/g) that is accompanied by fusion thereafter]

[3-2] according to aforementioned [3-1] described poly lactic acid series film or sheet, it further contains 0.5～15 weight part fluorine based polymer (B) with respect to 100 weight part poly(lactic acid) (A).

[3-3] according to aforementioned [3-2] described poly lactic acid series film or sheet, wherein, fluorine based polymer (B) is the tetrafluoroethylene based polymer.

[3-4] according to each described poly lactic acid series film or sheet among aforementioned [3-1]～[3-3], it further contains 0.1～15 weight part crystallization promoter (C) with respect to 100 weight part poly(lactic acid) (A).

[3-5] is according to each described poly lactic acid series film or sheet among aforementioned [3-1]～[3-4], it further contains 0.1～10 weight part acidic functionality modified olefin based polymer (D) with respect to 100 weight part poly(lactic acid) (A), and the acid value of described acidic functionality modified olefin based polymer (D) is that 10～70mgKOH/g, weight-average molecular weight are 10000～80000.

[3-6] according to each described poly lactic acid series film or sheet among aforementioned [3-1]～[3-5], and it is for by being melt into film or the sheet that the embrane method film forming obtains.

[3-7] according to aforementioned [3-6] described poly lactic acid series film or sheet, wherein, being melt into embrane method is rolling process.

[3-8] a kind of barrier film is characterized in that, it is for there being the barrier film of stripper processing layer at least one mask of barrier film base material, and this barrier film base material is to be made of each described poly lactic acid series film among aforementioned [3-1]～[3-7] or sheet.

[3-9] a kind of self adhesive tape or sheet is characterized in that, it is for having the self adhesive tape or the sheet of binder layer at least one mask of base material, and this base material is to be made of each described poly lactic acid series film among aforementioned [3-1]～[3-7] or sheet.

[3-10] a kind of protective film is characterized in that, it is for there being the protective film of releasable binder layer at least one mask of base material, and this base material is to be made of each described poly lactic acid series film among aforementioned [3-1]～[3-7] or sheet.

The effect of invention

Poly lactic acid series film of the present invention or sheet have following characteristic: even surpassing under 100 ℃ the high temperature, film or sheet can not fuse yet, be out of shape, in addition, at the inflexible that keeps script to have simultaneously, when the manufacturing of film or sheet, the man-hour of adding, when film or sheet are wound into the roller shape etc.,, can not produce fracture, cracking even apply tension force yet.Therefore, can utilize the biomass polymkeric substance in extensive fields, industrial meaning is very big.

In addition, barrier film of the present invention has following characteristic: even surpassing under 100 ℃ the high temperature, base material can not fuse yet, be out of shape, in addition, keeping the inflexible that originally has simultaneously, when the manufacturing of barrier film, the man-hour of adding, when being wound into the roller shape etc., even apply tension force, can not produce fracture, cracking yet.

And then, self adhesive tape of the present invention or sheet have following characteristic: have following characteristic: even surpassing under 100 ℃ the high temperature, base material can not fuse yet, be out of shape, in addition, keeping the inflexible that originally has simultaneously, when the manufacturing of self adhesive tape or sheet, the man-hour of adding, when being wound into the roller shape etc., even apply tension force, can not produce fracture, cracking yet.

Have again; protective film of the present invention has following characteristic: even surpassing under 100 ℃ the high temperature; base material can not fuse yet, be out of shape; in addition; keeping the inflexible that originally has simultaneously, when the manufacturing of protective film, the man-hour of adding, when being wound into the roller shape etc.; even apply tension force, can not produce fracture, cracking yet.

Description of drawings

Fig. 1 is the synoptic diagram that is illustrated in an example of the calendering film former that uses when making poly lactic acid series film of the present invention or sheet.

Fig. 2 is the synoptic diagram that is illustrated in an example of the polishing film former that uses when making poly lactic acid series film of the present invention or sheet.

Embodiment

[poly lactic acid series film or sheet]

Poly lactic acid series film of the present invention or sheet are for containing the resin film or the sheet of poly(lactic acid) (A).As the lactic acid of the starting monomer of poly(lactic acid) owing to having L type and the D type that there is optical isomer in chiral carbon atom.The poly(lactic acid) of using among the present invention (A) is with the lactic acid of the L type polymkeric substance as main component.The content of the lactic acid of the D type of sneaking into as impurity during manufacturing is few more, then can form high crystalline and dystectic polymkeric substance more, therefore, preferably uses the high lactic acid of L type purity as far as possible, and more preferably using L type purity is lactic acid more than 95%.In addition, poly(lactic acid) (A) can contain other copolymer compositions except lactic acid.

As aforementioned other copolymer compositions, for example can list ethylene glycol, propylene glycol, 1, polyol compounds such as ammediol, butyleneglycol, pentanediol, neopentyl glycol, hexylene glycol, heptanediol, ethohexadiol, nonanediol, decanediol, 1,4 cyclohexane dimethanol, glycerine, tetramethylolmethane, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, dihydroxyphenyl propane; Oxalic acid, propanedioic acid, pentanedioic acid, adipic acid, sebacic acid, nonane diacid, dodecanedioic acid, cyclohexane dicarboxylic acid, terephthalic acid, m-phthalic acid, phthalic acid, naphthalene dicarboxylic acids, two (to carboxyl phenyl) methane, anthracene dicarboxylic acid, 4,4 '-diphenyl ether dicarboxylic acid, m-phthalic acid 5-sodium sulfonate, m-phthalic acid-polycarboxylic acids such as 5-4-butyl-phosphonium; Hydroxycarboxylic acids such as oxyacetic acid, hydroxy-propionic acid, hydroxybutyric acid, hydroxypentanoic acid, hydroxycaproic acid, hydroxy-benzoic acid; Propiolactone, valerolactone, caprolactone, undecalactone, 1,5-Dioxepane-lactones such as 2-ketone.These copolymer compositions are preferably 0～30 mole of % with respect to the total monomer composition that constitutes poly(lactic acid) (A), more preferably 0～10 mole of %.

The weight-average molecular weight of poly(lactic acid) (A) is 10,000～400,000 for example, is preferably 50,000～300,000, more preferably 80,000～150,000.In addition, the melt flow rate (MFR) of poly(lactic acid) (A) under 190 ℃, load 21.2N [JIS K-7210(test conditions 4)] for example be 0.1～50g/10 minute, be preferably 0.2～20g/10 minute, more preferably 0.5～10g/10 minute, be preferably 1～7g/10 minute especially.When the value of aforementioned melt flow rate (MFR) is too high, characteristic, the poor heat resistance of the machinery of the film that obtains of film forming or sheet sometimes.In addition, the value of aforementioned melt flow rate (MFR) is crossed when low, and the load during film forming becomes too high sometimes.

Need to prove that in the present invention, " weight-average molecular weight " is meant the molecular weight of measuring with gel permeation chromatography (GPC) (polystyrene conversion).The condition determination of GPC is as described below.

Post: TSKgel SuperHZM-H/HZ2000/HZ1000

Column dimension: internal diameter 4.6mm * 150mm

Elutriant: chloroform

Flow: 0.3ml/min

Detector: RI

Column temperature: 40 ℃

Injection rate: 10 μ l

Manufacture method to poly(lactic acid) is not particularly limited, and as representational manufacture method, can list rac-Lactide method, direct polymerization method etc.The rac-Lactide method is following method: the condensation of lactic acid thermal dehydration is formed low-molecular-weight poly(lactic acid), with its thermal degradation under reduced pressure, thereby obtain rac-Lactide as the cyclic dimer of lactic acid, in the presence of stannous octoate metal salt catalysts such as (II), this rac-Lactide is carried out ring-opening polymerization, thereby obtain high molecular weight polylactic acid.In addition, the direct polymerization method is following method: under reduced pressure heat lactic acid in the phenyl ether equal solvent, the limit is removed the moisture limit and is made it polymerization in order to suppress hydrolysis, thereby directly obtains poly(lactic acid).

As poly(lactic acid) (A), can use the commercially available prod.As the commercially available prod, can list for example trade(brand)name " LACEA H-400 ", " LACEA H-100 " (above is Mitsui Chemicals, Inc's manufacturing), trade(brand)name " TERRAMAC TP-4000 ", " TERRAMAC TE-4000 " (the above UNITIKA LTD. of being manufacturing) etc.Certainly, as poly(lactic acid) (A), can use the poly(lactic acid) of making by known or habitual polymerization process (for example emulsion polymerization, solution polymerization process etc.).

From improving the viewpoint of biomass degree, the content of the poly(lactic acid) (A) in poly lactic acid series film of the present invention or the sheet is generally more than the 60 weight %, is preferably more than the 70 weight %, more preferably more than the 80 weight %, is preferably especially more than the 85 weight %.In addition, the upper limit of the content of aforementioned poly(lactic acid) (A) for example is 97 weight %, is preferably 95 weight %, more preferably 93 weight %.Here, the biomass degree is meant the ratio of the dry weight of employed biomass with respect to the dry weight of film or sheet.In addition, biomass be meant reproducible from biology organic property resource and do not contain fossil resource.

The fusion caloric receptivity Δ Hc ' of crystallization portion is for more than the 10J/g during film forming that poly lactic acid series film of the present invention or sheet are tried to achieve by following formula (1).

ΔHc′＝ΔHm-ΔHc （1）

[in the formula, Δ Hc is accompanied by the thermal discharge (J/g) of crystallization for film that measure by DSC, after the film forming or sheet at temperature-rise period, and Δ Hm is the caloric receptivity (J/g) that is accompanied by fusion thereafter]

Above-mentioned Δ Hc is that film or sheet are failed the thermal discharge of accompanying crystallizationization in the temperature-rise period in zone of crystallization when film forming, crystallization portion when Δ Hm is film forming and the caloric receptivity when the fusion of aforementioned temperature-rise period generates crystallization portion.These values are in the calorimetric measurement of DSC(differential scanning) in, with the area (heat) of crystalline exotherm peak, the form mensuration of fusing the area (heat) of endotherm(ic)peak.Δ Hc ' is for deducting the value that Δ Hc obtains from Δ Hm, is equivalent to the fusion caloric receptivity of the crystallization portion that generates when film forming.Therefore, Δ Hc ' becomes the crystallization degree of poly lactic acid series film or sheet and then becomes stable on heating index.

Δ Hc ' is the above poly lactic acid series film of 10J/g or the excellent heat resistance of sheet, even surpassing under 100 ℃ the high temperature (for example 120 ℃ or temperature more than it), film or sheet can not fuse yet, be out of shape.Therefore, can at high temperature process.Δ Hc ' is preferably more than the 12J/g, more preferably more than the 14J/g, is preferably more than the 15J/g especially.High more preferred more from the value of stable on heating viewpoint Δ Hc ', but the value of Δ Hc ' is when too high, film or sheet hardening, resistance to tearing reduces sometimes.Therefore, Δ Hc ' is preferably below the 40J/g, more preferably below the 35J/g, is preferably below the 30J/g especially.

In the present invention, in poly lactic acid series film or sheet, can use fluorine based polymer (B).Fluorine based polymer (B) for example is used as melt tension adjustment agent, crystallization promoter utilizes.As fluorine based polymer (B), for example can list tetrafluoroethylene based polymer, polychlorotrifluoroethylene, poly(vinylidene fluoride), fluorinated ethylene propylene etc.Fluorine based polymer (B) can use separately more than a kind or 2 kinds and be used in combination.As fluorine based polymer (B), especially can use tetrafluoroethylene based polymer (B ') aptly.

Aforementioned tetrafluoroethylene based polymer (B ') can be the homopolymer of tetrafluoroethylene, also can be tetrafluoroethylene and other monomeric multipolymers.As tetrafluoroethylene based polymer (B '), for example can list tetrafluoroethylene, PFA (multipolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether), fluorinated ethylene propylene copolymer (multipolymer of tetrafluoroethylene and R 1216), ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluor dioxole (perfluoro dioxole) multipolymer etc.In the middle of these, preferably polytetrafluoroethylene.Tetrafluoroethylene based polymer (B ') can use separately more than a kind or 2 kinds and be used in combination.

Fluorine based polymer (B) by the melt tension that makes the resin combination that contains poly(lactic acid) (A) improve, for example by being implemented in the crystallization that oriented crystallineization in the flow field that is melt into membrane process promotes poly(lactic acid) (A).In addition, if with fluorine based polymer (B) compounding in the resin combination that contains poly(lactic acid) (A), then can improve melt tension, and because melt viscosity also rises, therefore for example using under the film forming situation of stack, can prevent film forming resin combination when roller separates, produce extend, peel off bad.In addition, particularly tetrafluoroethylene based polymer fluorine based polymers such as (B ') also has the effect as the crystallization nucleating agent of poly(lactic acid) (A) simultaneously, therefore, be set near the crystallized temperature, can further promote poly(lactic acid) (A) crystallization by temperature with the resin combination after the firm film forming.Like this,, the crystallization of poly(lactic acid) (A) can be promoted,, the Δ Hc ' of poly lactic acid series film or sheet can be improved by like this by compounding fluorine based polymer (B) [especially tetrafluoroethylene based polymer (B ')].

Can think that the conduct of tetrafluoroethylene based polymer (B ') depends on the crystalline structure of tetrafluoroethylene based polymer (B ') at the effect of the crystallization nucleating agent of poly(lactic acid) (A).When carrying out the wide-angle x-ray diffraction, the interplanar distance of the lattice of poly(lactic acid) is 4.8 dusts, and is relative therewith, and the interplanar distance of tetrafluoroethylene based polymer (B ') is 4.9 dusts.Can think that thus tetrafluoroethylene based polymer (B ') can work as the crystallization nucleating agent of poly(lactic acid) (A) owing to have the epitaxy effect.Here, the epitaxy effect is meant: poly(lactic acid) (A) is in the growth of the surface crystallization of tetrafluoroethylene based polymer (B '), and poly(lactic acid) (A) is neatly in the mode of the high preferred orientation growth of the plane of crystal of tetrafluoroethylene based polymer (B ').

Tetrafluoroethylene based polymer (B ') though interplanar distance arranged by tetrafluoroethylene crystal habit partly, so interplanar distance is all identical.Therefore, so long as the crystal habit, rerum natura that can keep tetrafluoroethylene can great changes have taken place degree, just the amount to other monomer components in the multipolymer is not particularly limited, and the ratio of other monomer components in tetrafluoroethylene based polymer (B ') is to be ideal below the 5 weight % usually.

As tetrafluoroethylene based polymer (B '), can be the tetrafluoroethylene based polymer that obtains by any polymerization process, be preferably the tetrafluoroethylene based polymer that obtains by letex polymerization especially.Can think, the tetrafluoroethylene based polymer that obtains by letex polymerization is because fibrosis easily, therefore in poly(lactic acid) (A), form reticulated structure easily, the melt tension of the resin combination that contains poly(lactic acid) (A) is improved, help to promote effectively the crystallization of the poly(lactic acid) (A) in being melt into the flow field of membrane process.

In addition, for homodisperse in poly(lactic acid) (A), can for example use and use the so good polymkeric substance of the affinity with poly(lactic acid) (A) of (methyl) acrylic ester polymer to carry out the particle of the tetrafluoroethylene based polymer (B ') of modification.As this tetrafluoroethylene based polymer (B '), can list acrylic acid modified tetrafluoroethylene.

Weight-average molecular weight to fluorine based polymer (B) [tetrafluoroethylene based polymer (B ') etc.] is not particularly limited, and is generally 1,000,000～1,000 ten thousand, is preferably 2,000,000～8,000,000.

As fluorine based polymer (B) [tetrafluoroethylene based polymer (B ') etc.], can use the commercially available prod.For example, as the commercially available prod of tetrafluoroethylene, can list trade(brand)name " Fluon CD-014 " that Asahi Glass Co., Ltd makes, " Fluon CD-1 ", " Fluon CD-145 " etc.As the commercially available prod of acrylic acid modified tetrafluoroethylene, for example can list Mitsubishi Rayon Co., METABLEN A series such as the trade(brand)name " METABLEN A-3000 " that Ltd. makes, " METABLEN A-3800 ".

The content of the fluorine based polymer (B) in poly lactic acid series film or the sheet [the especially content of tetrafluoroethylene based polymer (B ')] is generally 0.5～15 weight part with respect to 100 weight part poly(lactic acid) (A), improve effect and keep the biomass degree and the such viewpoint of acquisition surface of good state from melt tension, be preferably 0.7～10 weight part, more preferably 1～5 weight part.The content of above-mentioned fluorine based polymer (B) [the especially content of tetrafluoroethylene based polymer (B ')] is when being lower than 0.5 weight part, be difficult to obtain the effect that melt tension improves, when surpassing 15 weight parts, can't obtain and the addition corresponding effects, in addition, the reduction of biomass degree can become problem.

In the present invention, become concrete method more than the 10J/g as the Δ Hc ' that makes poly lactic acid series film or sheet, for example can list: (1) is used and is rolled into embrane method etc. and be melt into the resin combination film forming that embrane method will contain poly(lactic acid) (A); (2) will be in poly(lactic acid) (A) compounding the resin combination film forming of crystallization promoter is arranged; (3) their combination etc.See below and state about being melt into embrane method.

As aforementioned crystallization promoter, can use the material the fluorine based polymer that in above-mentioned fluorine based polymer (B), can be used as crystallization promoter and utilize [for example tetrafluoroethylene based polymer (B ') etc.].As this crystallization promoter [being sometimes referred to as crystallization promoter (C)], so long as can confirm the material of the promoted effect of crystallization, just be not particularly limited, it is desirable to select to have material near the crystalline structure of the interplanar distance of the interplanar distance of the lattice of poly(lactic acid) (A).This be since the interplanar distance of the lattice of material more near the interplanar distance of the lattice of poly(lactic acid) (A), its effect as the crystallization nucleating agent of poly(lactic acid) (A) is high more.As such crystallization promoter (C), for example can list belong to organic system material polyphosphoric acid melamine, melamine cyanurate, phenyl-phosphonic acid zinc, phenyl-phosphonic acid calcium, phenyl-phosphonic acid magnesium, inorganic be the talcum, clay etc. of material.Wherein, the most approximate, the phenyl-phosphonic acid zinc that can obtain good crystallization facilitation effect of the interplanar distance of preferred interplanar distance and poly(lactic acid) (A).Crystallization promoter (C) can use separately more than a kind or 2 kinds and be used in combination.

As crystallization promoter (C), can use the commercially available prod.For example, as the commercially available prod of phenyl-phosphonic acid zinc, can list the trade(brand)name " ECOPROMOTE " of Misao Kusano's manufacturing etc.

The content of the crystallization promoter in poly lactic acid series film or the sheet (C) is generally 0.1～15 weight part with respect to 100 weight part poly(lactic acid) (A), and the viewpoint from more crystalline facilitation effect and biomass degree are kept is preferably 0.3～10 weight part.The content of above-mentioned crystallization promoter (C) is difficult to obtain the promoted effect of crystallization during less than 0.1 weight part, when surpassing 15 weight parts, can't obtain and the addition corresponding effects, and the reduction of biomass degree can become problem in addition.Wherein, as fluorine based polymer (B) being that the ratio of 0.5～15 weight part is used under the situation of tetrafluoroethylene based polymer (B ') with respect to 100 weight part poly(lactic acid) (A), the content of crystallization promoter (C) is generally 0.1～5 weight part with respect to 100 weight part poly(lactic acid) (A), viewpoint from more crystalline facilitation effect and biomass degree are kept is preferably 0.3～3 weight part.Under this situation, the content of above-mentioned crystallization promoter (C) is difficult to obtain the promoted effect of crystallization during less than 0.1 weight part, when surpassing 5 weight parts, can't obtain and the addition corresponding effects, and the reduction of biomass degree can become problem in addition.

The tear strength of poly lactic acid series film of the present invention or sheet is more than the 2.5N/mm on travel direction (MD direction), width (TD direction).Have the poly lactic acid series film of this tear strength or sheet when making this film or sheet, when this film of processing or sheet, apply the tensile operation, also can not produce fracture, ftracture even exist.In addition, add man-hour being wound into the roller shape or implementing Punching Technology etc., also can not produce fracture, ftracture.And then; if will have the poly lactic acid series film of this tear strength or the base material that sheet is used as barrier film, self adhesive tape or sheet, protective film etc.; then when making this barrier film, self adhesive tape or sheet, protective film etc.; when processing this barrier film, self adhesive tape or sheet, protective film etc.; apply the tensile operation even exist, also can not produce fracture, cracking.In addition, add man-hour they being wound into the roller shape or implementing Punching Technology etc., also can not produce fracture, ftracture.

In the present invention, aforementioned tear strength can be used the tear strength test machine, measures according to paper-tear strength test method-Elmendorf type tear tester method of JIS P8116.Tear strength is poly lactic acid series film or sheet more than the 2.5N/mm at travel direction (MD direction), width (TD direction), because as previously mentioned, not only when the manufacturing of this film or sheet, and when the roller shape is reeled, man-hour of adding etc. all can not produce fracture, cracking, therefore can carry out various processing, utilize the tremendous expansion of scope.

Tear strength all is preferably more than the 2.8N/mm at travel direction (MD direction), width (TD direction), more preferably more than the 3.2N/mm.Tear strength is high more preferred more.The upper limit as tear strength is not particularly limited, and for example can be generally below the 15N/mm for below the 20N/mm in addition for below the 30N/mm.

In the present invention, as the concrete method of the tear strength that makes poly lactic acid series film or sheet, for example can list the film forming method of resin combination that compounding in poly(lactic acid) (A) is had resistance to tearing properties-correcting agent (E) in above-mentioned scope.

As resistance to tearing properties-correcting agent (E), for example can list: (a) polyglycerol fatty acid ester and/or Polyglycerine condensation hydroxy fatty acid [being sometimes referred to as " polyglycerol fatty acid ester and/or Polyglycerine condensation hydroxy fatty acid (F) "], (b) has the nucleocapsid structure polymkeric substance [being sometimes referred to as " the nucleocapsid structure polymkeric substance (G) that has the grafting layer in the outside of granular rubber "] of grafting layer in the outside of granular rubber, (c) soft fatty family polyester [being sometimes referred to as " soft fatty family polyester (H) "] etc.These can use separately more than a kind or 2 kinds respectively and be used in combination.

In aforementioned (a) polyglycerol fatty acid ester and/or Polyglycerine condensation hydroxy fatty acid, polyglycerol fatty acid ester is the ester that Polyglycerine and fatty acid response obtain.Polyglycerine as the constituent of polyglycerol fatty acid ester for example can list two glycerine, triglycerin, four glycerine, five glycerine, six glycerine, seven glycerine, eight glycerine, nine glycerine, ten glycerine, 12 glycerine etc.They can use a kind or use as the mixture more than 2 kinds separately.The mean polymerisation degree of Polyglycerine is preferably 2～10.

Lipid acid as another constituent of polyglycerol fatty acid ester for example can use the lipid acid of carbon number more than 12.As the object lesson of lipid acid, can list lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, linolic acid, linolenic acid, eicosadienoic acid, timnodonic acid, mountain Yu acid, erucic acid, ricinolic acid, 12-oxystearic acid, hydrogenated castor seed oil lipid acid etc.They can use a kind or use as the mixture more than 2 kinds separately.

Polyglycerine condensation hydroxy fatty acid is the ester that Polyglycerine and condensation hydroxy aliphatic acid-respons obtain.Polyglycerine as the constituent of Polyglycerine condensation hydroxy fatty acid can list as the illustrative material of the constituent of aforementioned polyglycerol fatty acid ester.

The condensation hydroxy fatty acid of another constituent of Polyglycerine condensation hydroxy fatty acid is the condenses of hydroxy fatty acid.As aforementioned hydroxy fatty acid,, for example can list ricinolic acid, 12-oxystearic acid, hydrogenated castor seed oil lipid acid etc. so long as the lipid acid that has 1 above hydroxyl at intramolecularly gets final product.The condensation degree of condensation alcohol acid for example is more than 3, to be preferably 3～8.The condensation hydroxy fatty acid can use separately to mix more than a kind or 2 kinds and use.

As polyglycerol fatty acid ester, Polyglycerine condensation hydroxy fatty acid, can use the commercially available prod.As the commercially available prod of polyglycerol fatty acid ester, for example can list the trade(brand)name " CHIRABASOL VR-10 " that Taiyo Kagaku Co., Ltd. makes, CHIRABASOL series such as " CHIRABASOL VR-2 " etc.

Have in the nucleocapsid structure polymkeric substance of grafting layer in the outside of granular rubber at aforementioned (b), the granular rubber as constituting nuclear for example, can list acrylic rubber, butadiene-based rubber, organosilicon-acrylic acid series compounded rubber etc.In addition, as the polymkeric substance that constitutes shell, can list acrylic resins such as phenylethylene resin series, polymethylmethacrylate such as polystyrene etc.

The median size of aforementioned nucleocapsid structure polymkeric substance (aggregate of primary particle) for example is 50～500 μ m, is preferably 100～250 μ m.If its compounding is carried out melting mixing in poly(lactic acid) (A), then can form primary particle and dispersion.The average grain footpath of primary particle for example is 0.1～0.6 μ m.

As aforementioned nucleocapsid structure polymkeric substance, can use the commercially available prod.Commercially available prod as aforementioned nucleocapsid structure polymkeric substance, for example can list trade(brand)name Paraloid series (especially Paraloid EXL series), Mitsubishi Rayon Co. such as " Paraloid EXL2315 " that Rohm and Haas Japan K.K makes, METABLEN E types such as METABLEN C types such as METABLEN W type, " METABLEN C-223A ", " METABLEN E-901 " such as trade(brand)name METABLEN S such as " METABLEN S-2001 " type that Ltd. makes, " METABLEN W-450A " etc.

In aforementioned (c) soft fatty family polyester, can contain aliphatic polyester, aliphatic-aromatic copolyester.As (c) soft fatty family polyester (aliphatic polyester, aliphatic-aromatic copolyester), can list: obtain by polycarboxylic acids such as polyvalent alcohols such as dibasic alcohol and dicarboxylic acid, used aliphatic dihydroxy alcohol at least, used the polyester of aliphatic dicarboxylic acid as dicarboxylic acid at least as dibasic alcohol; The polymkeric substance of the aliphatic hydroxyl carboxylic acid of carbon number more than 4 etc.As aforementioned aliphatic dihydroxy alcohol, for example can list ethylene glycol, 1,2-propylene glycol, 1, ammediol, 2,2-dimethyl-1, ammediol, 1,2-butyleneglycol, 1,4-butyleneglycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexylene glycol, cyclohexanediol, 1, the aliphatic dihydroxy alcohol of carbon numbers such as 3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol 2～12 (comprising the ester ring type dibasic alcohol) etc.As aliphatic dicarboxylic acid, for example can list succsinic acid, propanedioic acid, pentanedioic acid, adipic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid, 1,3-cyclohexane dicarboxylic acid, 1, the saturated aliphatic dicarboxylic acids of carbon numbers such as 4-cyclohexane dicarboxylic acid 2～12 (comprising the ester ring type dicarboxylic acid) etc.At least used aliphatic dihydroxy alcohol, used at least as the dicarboxylic acid composition in the polyester of aliphatic dicarboxylic acid as glycol component aforementioned, the shared ratio of aliphatic dihydroxy alcohol for example is more than the 80 weight % in whole glycol component, be preferably more than the 90 weight %, more preferably more than the 95 weight %, remainingly can be aromatic diol etc.In addition, at least used aliphatic dihydroxy alcohol, used at least as the dicarboxylic acid composition in the polyester of aliphatic dicarboxylic acid as glycol component aforementioned, the shared ratio of aliphatic dicarboxylic acid for example is more than the 20 weight % in whole dicarboxylic acid compositions, be preferably more than the 30 weight %, more preferably more than the 50 weight %, remainingly can be aromatic dicarboxylic acid (for example being terephthalic acid etc.) etc.As the aliphatic hydroxyl carboxylic acid of aforementioned carbon number more than 4, for example can list the hydroxycarboxylic acid of carbon numbers such as hydroxybutyric acid, hydroxypentanoic acid, hydroxypentanoic acid, hydroxycaproic acid, hydroxydecanoic acid, hydroxyl dodecanoic acid 4～12 etc.(c) weight-average molecular weight of soft fatty family polyester (aliphatic polyester, aliphatic-aromatic copolyester) is 50,000～400,000 for example, is preferably 80,000～250,000.

As the representative example of (c) soft fatty family polyester, can list polybutylene succinate, poly-succsinic acid/hexanodioic acid-butanediol ester, polydiethylene glycol succinate, poly-succsinic acid/hexanodioic acid-glycol ester, poly-hexanodioic acid/terephthalic acid-butanediol ester, poly-sebacic acid/terephthalic acid-butanediol ester, PHA etc.

Can use the commercially available prod as (c) soft fatty family polyester.For example, as polybutylene succinate, can list the trade(brand)name " GS Pla AZ91T " that Mitsubishi chemical Co., Ltd makes, as poly-succsinic acid/hexanodioic acid-butanediol ester, can list the trade(brand)name " GS Pla AD92W " that Mitsubishi chemical Co., Ltd makes, as poly-hexanodioic acid/terephthalic acid-butanediol ester, can list the trade(brand)name " Ecoflex " that BASF JAPAN LTD. makes.

Viewpoint from the resistance to tearing modified effect, the content (total amount) of the aforementioned resistance to tearing properties-correcting agent (E) in poly lactic acid series film or the sheet is generally more than 1 weight part with respect to 100 weight part poly(lactic acid) (A), be preferably more than 1.5 weight parts, more preferably more than 2 weight parts.Wherein, when the amount of resistance to tearing properties-correcting agent (E) was too much, crystallization degree, crystallization speed easily reduced, thermotolerance also easily reduces and resistance to tearing properties-correcting agent (E) oozes out sometimes.From this point of view, the content (total amount) of the aforementioned resistance to tearing properties-correcting agent (E) in poly lactic acid series film or the sheet is preferably below 30 weight parts with respect to 100 weight part poly(lactic acid) (A), more preferably below 25 weight parts, more preferably below 20 weight parts, be preferably especially below 15 weight parts.

Need to prove, as resistance to tearing properties-correcting agent (E), using (a) polyglycerol fatty acid ester and/or Polyglycerine condensation hydroxy fatty acid (F) or (b) having under the situation of nucleocapsid structure polymkeric substance (G) of grafting layer in the outside of granular rubber, its content [total amount (a) or total amount (b)] is generally more than 1 weight part with respect to 100 weight part poly(lactic acid) (A) respectively, be preferably more than 1.5 weight parts, more preferably more than 2 weight parts.In addition,, be preferably below 20 weight parts, more preferably below 15 weight parts, more preferably below 12 weight parts, be preferably especially below 10 weight parts from above-mentioned viewpoint.In addition, using under the situation of (c) soft fatty family polyester (H) as resistance to tearing properties-correcting agent (E), its content is generally more than 5 weight parts with respect to 100 weight part poly(lactic acid) (A) respectively, is preferably more than 10 weight parts.In addition,, be preferably below 30 weight parts, more preferably below 25 weight parts, more preferably below 20 weight parts from above-mentioned viewpoint.

Have the nucleocapsid structure polymkeric substance (G) of grafting layer or (c) soft fatty family polyester (H) in the outside of granular rubber by in poly lactic acid series film or sheet, containing (a) polyglycerol fatty acid ester and/or Polyglycerine condensation hydroxy fatty acid (F), (b), can significantly improve the tear strength of poly lactic acid series film or sheet with above-mentioned scope.For example, the tear strength of poly lactic acid series film or sheet is more than the 2.5N/mm at travel direction (MD direction), width (TD direction).

Poly lactic acid series film of the present invention or sheet can also contain acidic functionality modified olefin based polymer (D) except above-mentioned composition.By compounding acidic functionality modified olefin based polymer (D) in poly(lactic acid) (A), can give the roller sliding.Therefore, with poly lactic acid series film of the present invention or sheet by formations molten state such as calendering film former and its space between metallic roll is passed through and during film forming, film or sheet can easily peel off from the surface of metallic roll, film forming successfully.Acidic functionality modified olefin based polymer (D) can use separately more than a kind or 2 kinds and be used in combination.

As the acidic functionality of acidic functionality modified olefin based polymer (D), for example can list carboxyl or derivatives thereof group etc.The derivatives group of carboxyl is meant chemically derived by carboxyl and group that obtain, for example can list anhydride group, ester group, amide group, imide, cyano group of carboxylic acid etc.In the middle of these, optimization acid's acid anhydride base.

Acidic functionality modified olefin based polymer (D) for example can grafting contain the unsaturated compound (following abbreviate as sometimes " unsaturated compound that contains acidic functionality ") of above-mentioned " acidic functionality " and obtain on the unmodified polyolefin based polymer.

As the unmodified polyolefin based polymer, can list the polyolefins or their the oligopolymer classes such as multipolymer of multipolymer, propylene and the alpha-olefin of high density polyethylene(HDPE), medium-density polyethylene, new LDPE (film grade), polypropylene, polybutene, poly--4-methylpentene-1, ethene and alpha-olefin; The polyolefin elastomerics classes such as blend of ethylene-propylene rubber(EPR), ethylene-propylene-diene copolymer rubber, isoprene-isobutylene rubber, divinyl rubber, low-crystalline ethylene-propylene copolymer, propene-1-butene copolymer, ethylene-vinyl ester copolymer, ethene-(methyl) methyl acrylate copolymer, ethene-(methyl) ethyl acrylate copolymer, ethene-copolymer-maleic anhydride, polypropylene and ethylene-propylene rubber(EPR); And their two or more miscellany etc.In the middle of these, the multipolymer of optimization polypropylene, propylene and alpha-olefin, new LDPE (film grade) and their oligopolymer class, special optimization polypropylene, propylene and the multipolymer of alpha-olefin and their oligopolymer class.As above-mentioned " oligopolymer class ", can list by reduce oligopolymer that method (molecular weight degradation) obtains by corresponding polymers etc. based on the pyrolysated molecular weight.The oligopolymer class also can obtain by polymerization.

As the unsaturated compound that contains acidic functionality, for example can list the unsaturated compound of carboxylic unsaturated compound, carboxylic derivatives group etc.As carboxylic unsaturated compound, for example can list toxilic acid, methylene-succinic acid, chloro methylene-succinic acid, chloromaleic acid, citraconic acid, (methyl) vinylformic acid etc.In addition, as the unsaturated compound of the derivatives group that contains carboxyl, for example can list the unsaturated compound that maleic anhydride, itaconic anhydride, chloro itaconic anhydride, chloromaleic acid acid anhydride, citraconic anhydride etc. contain the acid anhydride; (methyl) acrylate such as (methyl) methyl acrylate, (methyl) glycidyl acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester; (methyl) acrylamide, maleimide, (methyl) vinyl cyanide etc.In the middle of these, preferred carboxylic unsaturated compound, contain acid anhydride's unsaturated compound, more preferably contain the unsaturated compound of anhydride group, be preferably maleic anhydride especially.

The weight-average molecular weight of acidic functionality modified olefin based polymer (D) is 10000～80000th, and is important, is preferably 15000～70000, more preferably 20000～60000.This weight-average molecular weight less than 10000 less than the time, can be easy to become the reason of oozing out after film or sheet are shaped, surpass at 80000 o'clock, can be created in roller mixing in the isolating situation of poly(lactic acid) (A).Here, ooze out and be meant that through time lapse, low molecular weight compositions occurs to the phenomenon on film or sheet surface after film or sheet are shaped.

Acidic functionality in the acidic functionality modified olefin based polymer (D) can be bonded to the optional position of olefin polymer, its modification ratio is not particularly limited, the acid value of acidic functionality modified olefin based polymer (D) is generally 10～70mgKOH/g, is preferably 20～60mgKOH/g.This acid value can't obtain the raising effect of roller sliding during less than 10mgKOH/g, and when surpassing 70mgKOH/g, becoming is easy to cause the fouling of separating out on roller.Here, be meant in the fouling of separating out on the roller: when using metallic roll with resin combination fusion film forming, be compounded in composition in the resin combination or its oxidation, decomposition, chemical combination or deterioration product etc. adhere to or be piled up in the surface of metallic roll.Need to prove that in the present invention, " acid number " is meant the value of measuring according to the neutralization titration of JIS K0070-1992.

Acidic functionality modified olefin based polymer (D) obtains by make unmodified polyolefin based polymer and the unsaturated compound reaction that contains acidic functionality in the presence of organo-peroxide.As organo-peroxide, can use the general material that in radical polymerization, uses as initiator.Described reaction can be undertaken by any one method in solution method, the scorification.In solution method, be dissolved in the organic solvent and heating by mixture with organo-peroxide, thereby can obtain acidic functionality modified olefin based polymer (D) unmodified polyolefin based polymer and the unsaturated compound that contains acidic functionality.Temperature of reaction is preferably about 110～170 ℃.

In scorification, make it reaction by unmodified polyolefin based polymer and the mixture that contains the unsaturated compound of acidic functionality are mixed with organo-peroxide and carry out melting mixing, can obtain acidic functionality modified olefin based polymer (D) thus.Melting mixing can be carried out with various mixing machines such as forcing machine, Brabender mixing machine (Brabender mixer), kneader, Banbury mixers, and melting temperature is generally the temperature range of fusing point～300 ℃ of unmodified polyolefin based polymer.

Acidic functionality modified olefin based polymer (D) is preferably maleic anhydride modified polypropylene.As acidic functionality modified olefin based polymer (D), can use the commercially available prod, for example can list trade(brand)name " Umex1010 " (the maleic anhydride base modified polypropene that Sanyo Chemical Industries, Ltd. makes, acid value: 52mgKOH/g, weight-average molecular weight: 32000, modification ratio: 10 weight %), " Umex1001 " (maleic anhydride base modified polypropene, acid value: 26mgKOH/g, weight-average molecular weight: 49000, modification ratio: 5 weight %), " Umex2000 " (modified poly ethylene that contains the maleic anhydride base, acid value: 30mgKOH/g, weight-average molecular weight: 20000, modification ratio: 5 weight %) etc.

Content to the acidic functionality modified olefin based polymer (D) in poly lactic acid series film of the present invention or the sheet is not particularly limited, be generally 0.1～10 weight part with respect to 100 weight part poly(lactic acid) (A), never can separate out the persistence of the roller sliding effect of fouling on roller sets out with the viewpoint of keeping the biomass degree, be preferably 0.1～5 weight part, be preferably 0.3～3 weight part especially.The content of acidic functionality modified olefin based polymer (D) is difficult to obtain the roller sliding and improves effect during less than 0.1 weight part, when surpassing 10 weight parts, can't obtain and the addition corresponding effects, and in addition, the reduction of biomass degree can become problem.

Poly lactic acid series film of the present invention or sheet can contain various additives as required in the scope of harmless effect of the present invention.As this additive, can list antioxidant, UV light absorber, softening agent, stablizer, releasing agent, static inhibitor, tinting material (white pigment etc.), dripping inhibitor, fire retardant, anti hydrolysis agent, whipping agent, weighting agent etc.

Poly lactic acid series film of the present invention or sheet are owing to the degree height of crystallization, so solvent resistance is also excellent.For example, the swelling capacity of poly lactic acid series film of the present invention or sheet for example is below 2.5, to be preferably below 2.0 with respect to arbitrary solvent in vinyl acetic monomer, the toluene.Need to prove, swelling capacity can be measured by the following method: the sample (50mm * 50mm * thickness 0.05mm) of film or sheet is immersed in the solvent 15 minutes, the solvent on the surface of the sample of the film that takes out or sheet is removed with rag (waste rag), weight behind the dipping divided by the preceding weight of dipping, is measured thus.

In addition, poly lactic acid series film of the present invention or sheet also can be kept high level for characteristic, the elastic properties of machineries such as rigidity.For example, the initial elasticity modulus of poly lactic acid series film of the present invention or sheet is generally more than the 1000MPa at travel direction (MD direction), is preferably more than the 1500MPa.The upper limit of initial elasticity modulus is generally (for example for about 3000MPa) about 3500MPa at travel direction (MD direction).In addition, the breaking tenacity of poly lactic acid series film of the present invention or sheet is generally more than the 30MPa at travel direction (MD direction), is preferably more than the 35MPa.The upper limit of breaking tenacity is generally (for example for about 120MPa) about 150MPa.

And then the elongation of poly lactic acid series film of the present invention or sheet is generally more than 2.5% at travel direction (MD direction), is preferably more than 3.5%.The upper limit of elongation (for example about 12%) about travel direction (MD direction) is generally 15%.Wherein, using as resistance to tearing properties-correcting agent (E) under the situation of (c) soft fatty family polyester, the elongation of poly lactic acid series film or sheet is generally more than 5% at travel direction (MD direction), be preferably more than 10%, more preferably more than 20%, the upper limit of elongation is generally 150% at travel direction (MD direction), is preferably 120%, and more preferably 100%.

Need to prove that above-mentioned initial elasticity modulus, breaking tenacity, elongation are to use tensile testing machine, measure according to the test method of plastics-tensile properties of JIS K7161.

Device: tensile testing machine (Autograph AG-20kNG, Shimadzu Seisakusho Ltd. makes)

Specimen size: thickness 0.05mm * width 10mm * length 100mm(wherein, the mode of the travel direction when becoming forming thin film by the direction parallel with length direction (MD) is cut)

Condition determination:

Distance between chuck: 50mm

Draw speed: 300mm/min

Thick degree to poly lactic acid series film of the present invention or sheet is not particularly limited, and is generally 10～500 μ m, is preferably 20～400 μ m, more preferably 30～300 μ m.Poly lactic acid series film of the present invention or sheet can with the same purposes of normally used film or sheet in be extensive use of, can be aptly as the base material of self adhesive tape or sheet, in self adhesive tape or sheet etc. the base material, the base material of protective film etc. of the barrier film of use.

[manufacturing of poly lactic acid series film or sheet]

Be not particularly limited as the method for making poly lactic acid series film of the present invention or sheet, preferably will contain the film forming method of resin combination of poly(lactic acid) (A) by being melt into embrane method.If adopt and be melt into embrane method, the fusion of crystallization portion caloric receptivity Δ Hc ' becomes more than the 10J/g in the time of then can easily making film forming.

For example, poly lactic acid series film of the present invention or sheet can be made in the following way: by continuous fusion mixing roll that utilizes twin screw extruder etc. or the resin combination that contains poly(lactic acid) (A) that each composition homodisperse is formed by intermittent type melting mixing mechanism such as pressurization kneader, Banbury mixer, roll-type mixing rolls, and with it by extrusion molding or film forming such as rolling process, polishing (polishing) method such as T pattern head methods, blow moulding, cooling curing is made thus.As the aforementioned embrane method that is melt into, preferably, the resin combination by making molten state from the space between 2 metallic roll by and film forming is the method for desired thickness, preferred especially rolling process, polishing method.

By being melt into embrane method will contain the resin combination film forming of poly(lactic acid) (A) time, the temperature of this resin combination during to the fusion film forming (hereinafter referred to as the fusion film forming time resin temperature) is not particularly limited, the temperature the melting temperature (Tm) (Tm)-5 of the temperature that is preferably the crystallized temperature (Tc)+15 ℃ from the temperature-fall period of this resin combination in the temperature-rise period ℃.By being set at described temperature, can promote the crystallization of poly(lactic acid) (A), film of the present invention or sheet become and obtain thermotolerance easily.

For example, by rolling process during with this resin combination fusion film forming, the temperature the melting temperature (Tm) (Tm)-5 of the temperature that the temperature of this resin combination when stack is rolled (resin temperature when being equivalent to the fusion film forming) is set at the crystallized temperature (Tc)+15 ℃ from the temperature-fall period of this resin combination in the temperature-rise period ℃.Like this, by under the temperature below the fusing point, rolling, can promote oriented crystalline.This oriented crystalline facilitation effect can contain tetrafluoroethylene based polymer (B ') and raising more significantly by this resin combination.Can think that tetrafluoroethylene based polymer (B ') is to promote oriented crystallineization by its fibrillation in this resin combination, networking and with its synergy as the effect of crystallization nucleating agent.Therefore, by rolling in the said temperature scope, film of the present invention or sheet can obtain level and smooth condition of surface, and by the oriented crystalline facilitation effect, can realize good thermotolerance.

When making poly lactic acid series film of the present invention or sheet,, can possess the operation of the temperature condition after the control fusion film forming in order to make the crystallization facilitation effect of bringing by tetrafluoroethylene based polymer (B ') more effective.Particularly, can get off to promote crystalline operation (following abbreviate as sometimes " crystallization promotion operation ") to the temperature the crystallized temperature (Tc)+10 ℃ through the temperature by film forming this resin combination of fusion temporarily being remained on the crystallized temperature (Tc)-25 ℃ from the temperature-fall period of this resin combination, and then make its cooling curing.Promptly, crystallization promotes that operation is the temperature that film forming this resin combination of fusion is in be controlled at the crystallized temperature (Tc)-25 ℃ from the temperature-fall period of this resin combination by temperature to the operation of the state of the temperature the crystallized temperature (Tc)+10 ℃, is the operation that can promote the crystallization of this resin combination under the smooth-flat-surface state after the maintenance fusion film forming.This temperature-controlled process is not particularly limited, and for example can enumerating sends as an envoy to is melt into the method that this resin combination of film directly contacts with the roller that can be heated to specified temperature, band etc.

Especially, consider, it is desirable to, film forming this resin combination of fusion is contacted with the metallic roll of regulation surface temperature from the viewpoint that always is controlled at specified temperature.Therefore, in this operation, it is desirable to, make the resin combination that contains poly(lactic acid) (A) become the composition that to peel off from metallic roll simply, consider, the also preferred above-mentioned acidic functionality modified olefin based polymer (D) that adds from this viewpoint.

In addition, crystallization promotes that the time of operation is preferably long as far as possible, because it finally depends on the degree of crystallization of this resin combination and can't specify entirely, but is generally 2～10 seconds, is preferably 3～8 seconds.

Promote in the operation in above-mentioned crystallization, even because the interpolations of other crystallization nucleating agents etc. make the crystallized temperature (Tc) of resin combination in temperature-fall period change, also can be by measuring, hold the vertex temperature of the exothermic peak of the accompanying crystallizationization in the temperature-fall period in advance with differential scanning calorimetry device (DSC), thus the temperature condition that the suitableeest crystallization promotes operation can always be obtained.At this moment, the film that obtains by the heating under this temperature or the change of shape of sheet there is no need to consider substantially, and being preferably and making the caloric deformation rate that adds of gained film or sheet is temperature below 40%.

As the method for making poly lactic acid series film of the present invention or sheet, preferred following method, it is characterized in that, it is to comprise by being melt into embrane method containing the film forming method of resin combination of poly(lactic acid) (A), the temperature of this resin combination during the fusion film forming (resin temperature during the fusion film forming) is: the temperature the melting temperature (Tm) (Tm)-5 of the temperature of the crystallized temperature from the temperature-fall period of this resin combination (Tc)+15 ℃ in the temperature-rise period ℃, and/or the temperature of the crystallized temperature (Tc)-25 of film forming this resin combination of fusion in the temperature-fall period of this resin combination of associating ℃ is to the curing that is cooled after the crystallization of crystallized temperature (Tc)+10 ℃ promotes operation.

Promote in the manufacture method of poly lactic acid series film that operation contains or sheet in above-mentioned crystallization, owing to promote to advance in the operation crystallization of this resin combination to carry out cooling curing afterwards in crystallization, therefore be not easy residual internal stress, when the use of gained film or sheet, can not cause extreme thermal contraction.Therefore, near the fusing point of poly(lactic acid), can keep shape, also can use completely in the stable on heating purposes of unapplied needs so far with film forming high crystallized thin films of the present invention of above-mentioned manufacture method or sheet.And then owing to need once not heat so inefficient operation once more behind the cooling curing, therefore above-mentioned manufacture method is also deserving to be called very useful method aspect economy, the productivity.Wherein, can be before crystallization promotes operation and/or implement single shaft or biaxial stretch-formed processing (preferred biaxial stretch-formed processing) afterwards.By implementing stretch processing, can further improve crystallization sometimes.The stretch processing temperature for example is 60～100 ℃.

Promote the poly lactic acid series film that operation contains or the manufacture method of sheet as above-mentioned crystallization, proceed to the mode of crystallization promotion operation, cooling curing operation continuously owing to can shorten the treatment time from being melt into membrane process, therefore consider it is ideal from the viewpoint of productivity.As this method, can list the method for using calendering film former, polishing film former etc.

[calendering film forming]

Fig. 1 is the synoptic diagram that is illustrated in 1 example of the calendering film former that uses in the described manufacture method.Below describe Fig. 1 in detail.

The resin combination of calendering molten state makes its attenuation gradually between 4 stacks that are called the 1st roller the 1, the 2nd roller the 2, the 3rd roller the 3, the 4th roller 4, finally between the 3rd roller 3 and the 4th roller 4 by the time be prepared into desired thickness.When the calendering film forming, the film forming of the resin combination at the 1st roller 1～the 4th roller 4 places is equivalent to " being melt into membrane process ".In addition, the temperature that is set at the crystallized temperature (Tc)-25 ℃ from the temperature-fall period of this resin combination is to roller groups of film forming these resin combination 8 initial contacts of outlet roller 5 expression fusions of the temperature the crystallized temperature (Tc)+10 ℃, constitute performance is peeled off this resin combination 8 of molten state from the 4th roller 4 effect by the roller group that (among Fig. 1 is 3) more than 1 or 2.Like this, outlet roller 5 is made of a plurality of rollers, can carry out respectively under the thermoregulator situation of each roller, and the temperature of each roller is preferably identical, but as long as in temperature required scope, also can be different.The radical of outlet roller 5 for a long time, the isothermal crystal time is elongated, for promoting that crystallization is favourable.When the calendering film forming, at outlet roller 5 places, the crystallization of film forming this resin combination 8 of fusion obtains promoting, so this resin combination 8 is equivalent to " crystallization promotion operation " from the operation that outlet roller 5 passes through.

Two cooling rollers 6 and the following effect of 7 performances: by make this resin combination 8 between them by and with these resin combination 8 coolings, curing, and be desired shape with its surface forming.Therefore, usually, a roller (for example cooling roller 6) is a metallic roll, and the roller surface carried out design for the surface shape that forms this resin combination 8, as another root roller (for example cooling roller 7), uses rubber rollers.Need to prove that the arrow among the figure is represented the sense of rotation of roller.9 are spacer gel (resin is deposited glue).

[polishing film forming]

Fig. 2 is the synoptic diagram that is illustrated in 1 example of the polishing film former that uses in the described manufacture method.Below describe Fig. 2 in detail.

The forcing machine leading section 10 of forcing machine (not shown) is configured between warmed-up the 2nd roller 2 and the 3rd roller 3, under predefined extruded velocity, between the 2nd roller 2 and the 3rd roller 3, extrudes the resin combination 8 of molten state continuously.The resin combination of being extruded 8 is rolled and attenuation between the 2nd roller 2 and the 3rd roller 3, finally between the 3rd roller 3 and the 4th roller 4 by the time be prepared to desired thickness.When the polishing film forming, the film forming of the resin combination 8 at the 2nd roller 2～the 4th roller 4 places is equivalent to " being melt into membrane process ".After this, three outlet rollers 5 of the temperature from the temperature that is set at the crystallized temperature (Tc)-25 ℃ from the temperature-fall period of this resin combination 8 to crystallized temperature (Tc)+10 ℃ [preferred crystallized temperature (Tc) ± 10 ℃] pass through, pass through from cooling roller 6 and 7 at last, make solidified film or sheet thus.In polishing during film forming, the operation by outlet roller 5 is equivalent to " crystallization promotion operation ".

Film of the present invention or sheet as previously mentioned, can with the same purposes of normally used film or sheet in be extensive use of but the base material of base material, protective film or the sheet of suitable especially base material, adhesive sheet or band as barrier film (release liner).

[barrier film]

Barrier film of the present invention is characterised in that it is for there being the barrier film of stripper processing layer at least one mask of barrier film base material, and this barrier film base material is made of aforesaid poly lactic acid series film or sheet.

Stripper (releasing agent) as using in order to form aforementioned stripper processing layer is not particularly limited, and for example can use silicon-type stripper, fluorine series stripping agent, long-chain alkyl groups series stripping agent, polyolefin stripper etc.Stripper can use separately more than a kind or 2 kinds and be used in combination.

In addition, as stripper, so long as can when forming the separability that tunicle and this tunicle are being brought into play and purposes is appropriate accordingly on the barrier film base material, can not produce dysgenic stripper to tackiness agent, just be not particularly limited, for example, from making its viewpoint, preferably can form peeling force with respect to this adhesive face and be the stripper of the tunicle that (is preferably about 0.1～10N/50mm) about 0～25N/50mm to excellent peel property such as performance such as the adhesive face of self adhesive tape or sheet etc.

In the middle of aforementioned stripper, from aspects such as stripping performances, preferred organosilicon series stripping agent.As the silicon-type stripper, be not particularly limited, as its representational material, can list thermoset add-on type silicon-type stripper (thermoset addition type polysiloxane series stripping agent).

Thermoset add-on type silicon-type stripper will contain the organopolysiloxane (organosilicon that contains alkenyl) of alkenyl and contain the organopolysiloxane of hydrosilyl groups as necessary constituent as functional group in molecule as functional group in molecule.

As the above-mentioned organopolysiloxane that in molecule, contains alkenyl, particularly preferably in the organopolysiloxane that has 2 above alkenyls in the molecule as functional group.As above-mentioned alkenyl, for example can list vinyl (ethenyl group), allyl group (2-propenyl), butenyl, pentenyl, hexenyl etc.Need to prove, above-mentioned alkenyl usually with the Siliciumatom of the organopolysiloxane that forms main chain or skeleton (for example the Siliciumatom of Mo Duan Siliciumatom, main chain inside etc.) bonding.

In addition, as the above-mentioned organopolysiloxane that is formed with main chain or skeleton, the multipolymer [for example poly-(dimethyl siloxane-di-ethyl siloxane) etc.] etc. that for example can list poly-alkyl-alkyl siloxanes (polydialkysiloxane), polyoxyethylene alkyl aryl radical siloxane such as polydimethylsiloxane, poly-di-ethyl siloxane, polymethy ethylsiloxane and use the monomer component of multiple silicon atoms.Wherein, polydimethylsiloxane suits.That is, as the organopolysiloxane that in molecule, contains alkenyl as functional group, particularly, but preference illustrate have vinyl, hexenyl etc. is as the polydimethylsiloxane of functional group.

About the above-mentioned organopolysiloxane linking agent that in molecule, contains hydrosilyl groups as functional group, it is for have the organopolysiloxane with the hydrogen atom (Siliciumatom that especially has the Si-H key) of silicon atom bonding in molecule, particularly preferably in having the organopolysiloxane that has the Siliciumatom of Si-H key more than 2 in the molecule.As above-mentioned Siliciumatom with Si-H key, for the Siliciumatom in the main chain, in the side chain Siliciumatom all can, that is, the structural unit that can be used as main chain contains, the structural unit that perhaps also can be used as side chain contains.Wherein, the quantity of the Siliciumatom of Si-H key is so long as just be not particularly limited more than 2.As the above-mentioned organopolysiloxane linking agent that contains hydrosilyl groups in molecule as functional group, particularly, polymethyl hydrogen siloxane, poly-(dimethyl siloxane-methyl hydrogen siloxane) etc. suit.

In stripper of the present invention, for the storage stability of giving under the room temperature can use reaction suppressor.For example, using under the situation of thermoset add-on type silicon-type stripper as stripper, particularly, for example can list 3,5-dimethyl-1-hexin-3-alcohol, 3-Methyl-1-pentene-3-alcohol, 3-methyl-pirylene, 3,5-dimethyl-3-hexene-1-alkynes etc.

In addition, in stripper, except mentioned component, can also use release control agent etc. as required.For example, using under the situation of thermoset add-on type silicon-type stripper as stripper, particularly can add release control agents such as MQ resin, not have the organopolysiloxane (trimethylsiloxy end-capped polydimethylsiloxane etc.) of alkenyl or hydrosilyl groups etc.The content of these compositions in thermoset add-on type silicon-type stripper is not particularly limited, is preferably 1～30 weight %.

And then, in stripper, can use various additives as required.As the additive that can use as required, for example can weighting agent, static inhibitor, antioxidant, UV light absorber, softening agent, tinting material (dyestuff, pigment etc.) etc. be shown example.

The formation of stripper processing layer can be undertaken by known or customary way.For example can list the remover combination that will contain stripper be coated on the barrier film base material (under the situation that has the middle layer on the barrier film base material for this middle layer) on method etc.Coating can be by in the formation of common lift-off processing layer, using coating machine, forcing machine, printing press etc. carry out.

As the thickness of stripper processing layer, can suitably select according to purposes etc., for example be 0.02～1 μ m, be preferably 0.05～0.7 μ m, more preferably about 0.1～0.5 μ m.

Barrier film of the present invention can have other layers (middle layer) as required between barrier film base material and stripper processing layer.

[self adhesive tape or sheet]

Self adhesive tape of the present invention or sheet are characterised in that it is for having the self adhesive tape or the sheet of binder layer at least one mask of base material, and this base material is made of aforesaid poly lactic acid series film or sheet.

In the present invention, on the surface of aforementioned substrates, can be as required in order to improve the scorching exposure of for example chromic acid processing of surface treatment, ozone exposure, fire implementing to habitually practise with the adaptation of the layer of adjacency, high-voltage electric shock exposure, the processing of ionization radiation etc. based on the oxide treatment of chemistry or physical method etc.

As the tackiness agent that constitutes aforementioned adhesion agent layer, be not particularly limited, for example can be used in combination more than a kind or 2 kinds rubber and to be tackiness agent, acrylic adhesive, vinyl alkyl ethers and be tackiness agent, silicon-type tackiness agent, polyester and be tackiness agent, polyamide-based tackiness agent, polyurethane series tackiness agent, vinylbenzene-diene block copolymer be tackiness agent, in these tackiness agents compounding fusing point be the known tackiness agents such as creep properties modified form tackiness agent of about hot melt property resin below 200 ℃.Tackiness agent can be for solvent-borne type, emulsion-type, hot-melting type, energy ray-curable tackiness agent, add known any tackiness agents such as heat-releasable.

Usually, as the aforementioned adhesion agent, can use natural rubber, various synthetic rubber is tackiness agent as the rubber of base polymer; To use the acrylic adhesive that the acrylic acid polymer (homopolymer or multipolymer) of (methyl) alkyl acrylate obtains as base polymer more than a kind or 2 kinds etc. as monomer component.Especially preferably use in the present invention the acrylic adhesive of acrylic acid polymer as base polymer.

(methyl) alkyl acrylate as the monomer component that can be used as aforementioned acrylic acid polymer for example can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) isodecyl acrylate, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid pentadecyl ester, (methyl) vinylformic acid cetyl ester, (methyl) vinylformic acid heptadecyl ester, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid nonadecyl ester, (methyl) vinylformic acid C such as (methyl) vinylformic acid eicosyl ester _1-20Alkyl ester etc.

Aforementioned acrylic acid polymer is with the purpose that is modified as of force of cohesion, thermotolerance, bridging property etc., as required, can contain with can with the corresponding unit of other monomer components of aforementioned (methyl) alkyl acrylate copolymer.As this monomer component, for example can list (methyl) acrylate that (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid cyclohexyl methyl esters, (methyl) vinylformic acid norbornene ester etc. have the aliphatics cyclic skeleton; (methyl) phenyl acrylate, (methyl) benzyl acrylate etc. have (methyl) acrylate of aromatic carbon ring; Carboxylic monomers such as vinylformic acid, methacrylic acid, vinylformic acid carboxyl ethyl ester, vinylformic acid carboxyl pentyl ester, methylene-succinic acid, toxilic acid, fumaric acid, Ba Dousuan; Maleic anhydride, itaconic anhydride etc. contain the monomer of anhydride group; The monomer of hydroxyls such as (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester, the own ester of (methyl) vinylformic acid hydroxyl, (methyl) vinylformic acid hydroxyl monooctyl ester, (methyl) vinylformic acid hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid hydroxyl lauryl, methacrylic acid (4-methylol cyclohexyl) methyl esters; Styrene sulfonic acid, allyl sulphonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic acid, (methyl) acrylamide propane sulfonic acid, (methyl) vinylformic acid sulfonic group propyl ester, (methyl) acryloxy naphthene sulfonic acid etc. contain sulfonic monomer; (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-butyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxymethyl-propane (methyl) acrylamide etc. contain the monomer of (N-replacement) acid amides system; (methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid N, (methyl) acrylic-amino alkyl esters such as N-dimethylamino ethyl ester, (methyl) vinylformic acid tertiary butyl amino ethyl ester are monomer; (methyl) alkoxyalkyl acrylates such as (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid ethoxy ethyl ester are monomer; Maleimides such as N-cyclohexyl maleimide, N-sec.-propyl maleimide, N-lauryl maleimide, N-phenylmaleimide are monomer; Clothing health imide series monomers such as N-methyl clothing health imide, N-ethyl clothing health imide, N-butyl clothing health imide, N-octyl group clothing health imide, N-2-ethylhexyl clothing health imide, N-cyclohexyl clothing health imide, N-lauryl clothing health imide; The N-(methyl) acryloyl-oxy methylene succinimide, N-(methyl) acryl-6-oxa-hexa-methylene succinimide, N-(methyl) acryl-succinimides such as 8-oxa-eight methylene radical succinimides are monomer; Ethene base system monomers such as vinyl acetate between to for plastic base ester, vinyl propionate base ester, N-vinyl pyrrolidone, methyl ethylene pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinylpyrazine, vinyl pyrrole, vinyl imidazole, second alkene base oxazole, vinyl morpholine, N-vinyl carboxylic acid amides, vinylbenzene, alpha-methyl styrene, N-caprolactam; The monomer of cyano-containing such as vinyl cyanide, methacrylonitrile; (methyl) glycidyl acrylate etc. contains the acrylic monomer of epoxy group(ing); Glycol such as (methyl) polyalkylene glycol acrylate ester, (methyl) vinylformic acid polypropylene glycol ester, (methyl) vinylformic acid methoxyl group glycol ester, (methyl) vinylformic acid methoxyl group polypropylene glycol ester are acrylate monomer; The N-(methyl) acryloyl morpholine, (methyl) tetrahydrofurfuryl acrylate, fluoridize the acrylic ester monomer that (methyl) acrylate, organosilicon (methyl) acrylate etc. have heterocycle, halogen atom, Siliciumatom etc.; Polyfunctional monomers such as hexylene glycol two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate; Ethylene series monomers such as isoprene, divinyl, iso-butylene; Vinyl ether such as vinyl ether are monomer etc.These monomer components can use separately or be used in combination more than 2 kinds.

Acrylic acid polymer can be by manufacturings such as known radical polymerization such as solution polymerization, mass polymerization, letex polymerizations.Acrylic acid polymer is that random copolymers, segmented copolymer, graftomer etc. all can.In polymerization, can use normally used polymerization starter, chain-transfer agent.

The weight-average molecular weight that constitutes the base polymer of tackiness agent is 10,000～2,000,000 for example, is preferably 300,000～1,500,000.If the weight-average molecular weight of base polymer is low excessively,, be easy to produce pollutions such as cull at the adherend place though, for example heating under the situation about peeling off then in excellence aspect the tracing ability of adherend.On the other hand, if the weight-average molecular weight of base polymer is too high, then the tracing ability to adherend easily reduces.

In tackiness agent, except base polymer, as required, (epoxy is a linking agent can also to contain linking agent, the isocyanate-based linking agent, trimeric cyanamide is that linking agent oxazoline is a linking agent, aziridine is a linking agent, metal-chelating compounds etc.), crosslinking accelerator (crosslinking catalyst), tackifier (rosin derivative resin for example, polyterpene resin, petroleum resin, soluble phenolic resin etc.), thickening material, softening agent, weighting agent, whipping agent, antiaging agent, antioxidant, UV light absorber, static inhibitor, tensio-active agent, flow agent, tinting material, fire retardant, suitable additive such as silane coupling agent.

The formation of binder layer can be undertaken by known or customary way.For example can list with binder composition be coated on base material (under the situation that has the middle layer on the base material for this middle layer) on method; Binder composition is coated on the suitable barrier film forms binder layer, then with the method for this binder layer transfer printing (moving) to the base material (being this middle layer under the situation that has the middle layer on the base material) etc.Coating can be by in the formation of common binder layer, using coating machine, forcing machine, printing press etc. carry out.

As the thickness of binder layer, can suitably select according to purposes etc., for example be 5～3000 μ m, be preferably about 10～500 μ m.

The bounding force of binder layer under 25 ℃ (peeled off (peel) for 180 °, for pet film, draw speed 300mm/ minute) can be according to purposes (weak adhesion type, strong adhesion type etc.) wait suitably selection, for example be more than the 3.0N/20mm, to be preferably more than the 5.0N/20mm, more preferably more than the 7.0N/20mm, under the situation of strong adhesion type, more preferably more than the 10.0N/20mm.

Self adhesive tape of the present invention or sheet can have other layers (middle layer: for example elastic layer, rigid layer etc.) as required between base material and binder layer.In addition, on binder layer, during till using self adhesive tape or sheet, can be provided for protecting the barrier film of binder layer.

[protective film]

Protective film of the present invention is characterised in that it is for there being the protective film of releasable binder layer at least one mask of base material, and this base material is made of aforesaid poly lactic acid series film or sheet.

In the present invention, on the surface of aforementioned substrates, can be as required in order to improve the scorching exposure of for example chromic acid processing of surface treatment, ozone exposure, fire implementing to habitually practise with the adaptation of the layer of adjacency, high-voltage electric shock exposure, the processing of ionization radiation etc. based on the oxide treatment of chemistry or physical method etc.

As the tackiness agent that constitutes aforementioned releasable binder layer, be not particularly limited, for example can be used in combination more than a kind or 2 kinds rubber and to be tackiness agent, acrylic adhesive, vinyl alkyl ethers and be tackiness agent, silicon-type tackiness agent, polyester and be tackiness agent, polyamide-based tackiness agent, polyurethane series tackiness agent, vinylbenzene-diene block copolymer be tackiness agent, in these tackiness agents compounding fusing point be the known tackiness agents such as creep properties modified form tackiness agent of about hot melt property resin below 200 ℃.As long as tackiness agent has releasable, just can be the known tackiness agents of releasable arbitrarily such as solvent-borne type, emulsion-type, hot-melting type.

Usually, as aforementioned releasable tackiness agent, can use natural rubber, various synthetic rubber is tackiness agent as the rubber of base polymer; The acrylic acid polymer (homopolymer or multipolymer) that will use (methyl) alkyl acrylate more than a kind or 2 kinds as monomer component is as acrylic adhesive of base polymer etc.Especially preferably use in the present invention the acrylic adhesive of acrylic acid polymer as base polymer.

(methyl) alkyl acrylate as the monomer component that can be used as aforementioned acrylic acid polymer for example can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) isodecyl acrylate, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid pentadecyl ester, (methyl) vinylformic acid cetyl ester, (methyl) vinylformic acid heptadecyl ester, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid nonadecyl ester, (methyl) vinylformic acid C such as (methyl) vinylformic acid eicosyl ester _1-20Alkyl ester etc.

Aforementioned acrylic acid polymer is with the purpose that is modified as of force of cohesion, thermotolerance, bridging property etc., can contain as required with can with the corresponding unit of other monomer components of aforementioned (methyl) alkyl acrylate copolymer.As this monomer component, for example can list (methyl) acrylate that (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid cyclohexyl methyl esters, (methyl) vinylformic acid norbornene ester etc. have the aliphatics cyclic skeleton; (methyl) phenyl acrylate, (methyl) benzyl acrylate etc. have (methyl) acrylate of aromatic carbon ring; Carboxylic monomers such as vinylformic acid, methacrylic acid, vinylformic acid carboxyl ethyl ester, vinylformic acid carboxyl pentyl ester, methylene-succinic acid, toxilic acid, fumaric acid, Ba Dousuan; Maleic anhydride, itaconic anhydride etc. contain the monomer of anhydride group; The monomer of hydroxyls such as (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester, the own ester of (methyl) vinylformic acid hydroxyl, (methyl) vinylformic acid hydroxyl monooctyl ester, (methyl) vinylformic acid hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid hydroxyl lauryl, methacrylic acid (4-methylol cyclohexyl) methyl esters; Styrene sulfonic acid, allyl sulphonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic acid, (methyl) acrylamide propane sulfonic acid, (methyl) vinylformic acid sulfonic group propyl ester, (methyl) acryloxy naphthene sulfonic acid etc. contain sulfonic monomer; (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-butyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxymethyl-propane (methyl) acrylamide etc. contain the monomer of (N-replacement) acid amides system; (methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid N, (methyl) acrylic-amino alkyl esters such as N-dimethylamino ethyl ester, (methyl) vinylformic acid tertiary butyl amino ethyl ester are monomer; (methyl) alkoxyalkyl acrylates such as (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid ethoxy ethyl ester are monomer; Maleimides such as N-cyclohexyl maleimide, N-sec.-propyl maleimide, N-lauryl maleimide, N-phenylmaleimide are monomer; Clothing health imide series monomers such as N-methyl clothing health imide, N-ethyl clothing health imide, N-butyl clothing health imide, N-octyl group clothing health imide, N-2-ethylhexyl clothing health imide, N-cyclohexyl clothing health imide, N-lauryl clothing health imide; The N-(methyl) acryloyl-oxy methylene succinimide, N-(methyl) acryl-6-oxa-hexa-methylene succinimide, N-(methyl) acryl-succinimides such as 8-oxa-eight methylene radical succinimides are monomer; Ethene base system monomers such as vinyl acetate between to for plastic base ester, vinyl propionate base ester, N-vinyl pyrrolidone, methyl ethylene pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinylpyrazine, vinyl pyrrole, vinyl imidazole, second alkene base oxazole, vinyl morpholine, N-vinyl carboxylic acid amine, vinylbenzene, alpha-methyl styrene, N-caprolactam; The monomer of cyano-containing such as vinyl cyanide, methacrylonitrile; (methyl) glycidyl acrylate etc. contains the acrylic monomer of epoxy group(ing); Glycol such as (methyl) polyalkylene glycol acrylate ester, (methyl) vinylformic acid polypropylene glycol ester, (methyl) vinylformic acid methoxyl group glycol ester, (methyl) vinylformic acid methoxyl group polypropylene glycol ester are acrylate monomer; The N-(methyl) acryloyl morpholine, (methyl) tetrahydrofurfuryl acrylate, fluoridize the acrylic ester monomer that (methyl) acrylate, organosilicon (methyl) acrylate etc. have heterocycle, halogen atom, Siliciumatom etc.; Polyfunctional monomers such as hexylene glycol two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate; Ethylene series monomers such as isoprene, divinyl, iso-butylene; Vinyl ether such as vinyl ether are monomer etc.These monomer components can use separately or be used in combination more than 2 kinds.

Acrylic acid polymer can be by manufacturings such as known radical polymerization such as solution polymerization, mass polymerization, letex polymerizations.Acrylic acid polymer is that random copolymers, segmented copolymer, graftomer etc. all can.In polymerization, can use normally used polymerization starter, chain-transfer agent.

The weight-average molecular weight that constitutes the base polymer of tackiness agent is 10,000～5,000,000 for example, is preferably 20,000～1,000,000.If the weight-average molecular weight of base polymer is low excessively, though, easily produce pollutions such as cull at the adherend place peeling off the back more then in excellence aspect the tracing ability of adherend.On the other hand, if the weight-average molecular weight of base polymer is too high,, the tracing ability of adherend is easily reduced though then the adherend place after peeling off is again reduced by the pollution that cull etc. brings.

In tackiness agent, except base polymer, (epoxy is a linking agent can also to contain linking agent as required, the isocyanate-based linking agent, trimeric cyanamide is that linking agent oxazoline is a linking agent, aziridine is a linking agent, metal-chelating compounds etc.), crosslinking accelerator (crosslinking catalyst), tackifier (rosin derivative resin for example, polyterpene resin, petroleum resin, soluble phenolic resin etc.), thickening material, softening agent, weighting agent, whipping agent, antiaging agent, antioxidant, UV light absorber, static inhibitor, tensio-active agent, flow agent, tinting material, fire retardant, suitable additive such as silane coupling agent.Especially, in order to give the tackiness agent releasable, preferably add linking agent.

The formation of releasable binder layer can be undertaken by known or customary way.For example can list with binder composition be coated on base material (under the situation that has the middle layer on the base material for this middle layer) on method; Binder composition is coated on the suitable barrier film forms binder layer, then with the method for this binder layer transfer printing (moving) to the base material (being this middle layer under the situation that has the middle layer on the base material) etc.Coating can be by in the formation of common binder layer, using coating machine, forcing machine, printing press etc. carry out.

As the thickness of releasable binder layer, can suitably select according to purposes etc., for example be 1～100 μ m, be preferably about 1～50 μ m.

The bounding force of releasable binder layer under 25 ℃ (peel off (peel) for 180 °, for pet film, draw speed 300mm/ minute) is as long as in the scope of removable, for example less than 3N/20mm.Lower limit for example is about 0.01N/20mm.

Protective film of the present invention can have other layers (middle layer) as required between base material and releasable binder layer.In addition, on the releasable binder layer, during till using protective film, can be provided for protecting the barrier film of releasable binder layer.

Embodiment

Below enumerate embodiment and comparative example and further specify the present invention.The present invention is not subjected to their any qualification.Need to prove that the evaluation among the embodiment etc. is following to be carried out.

Be illustrated in the middle materials that use such as embodiment below.

＜poly(lactic acid) (A)＞

A1: trade(brand)name " TERRAMAC TP-4000 " (UNITIKA LTD. manufacturing)

＜fluorine based polymer (B)＞

B1: acrylic acid modified tetrafluoroethylene (Ltd. makes for trade(brand)name " METABLEN A-3000 ", Mitsubishi Rayon Co.)

＜crystallization promoter (C)＞

C1: phenyl-phosphonic acid zinc (trade(brand)name " ECOPROMOTE ", Nissan Chemical Ind Ltd makes)

＜acidic functionality modified olefin based polymer (D)＞

D1: the modified polypropene (weight-average molecular weight 32000, acid value 52mgKOH/g, trade(brand)name " Umex1010 ", Sanyo Chemical Industries, Ltd.'s manufacturing) that contains the maleic anhydride base

＜resistance to tearing properties-correcting agent (E)＞

E1: polyglycerol fatty acid ester (Taiyo Kagaku Co., Ltd. makes for number-average molecular weight Mn1000, trade(brand)name " CHIRABASOL VR-10 ")

E2: polyglycerol fatty acid ester (Taiyo Kagaku Co., Ltd. makes for number-average molecular weight Mn1700, trade(brand)name " CHIRABASOL VR-2 ")

E3: nucleocapsid structure polymkeric substance (Rohm and Haas Japan K.K makes for acrylic rubber/polymethylmethacrylate-styrene core shell structure polymkeric substance, trade(brand)name " Paraloid EXL2315 ")

E4: soft fatty family polyester (BASF JAPAN LTD. makes for poly-hexanodioic acid/terephthalic acid-butanediol ester, trade(brand)name " Ecoflex ")

Example I-1

Prepare resin combination in the compounding ratio shown in the following table 1, carry out melting mixing with Banbury mixer, rolling film forming to thickness with inverted L shape 4 roll calendars then becomes 50 μ m(and is melt into membrane process).Then, as shown in Figure 1, after being melt into membrane process, and then dispose 3 rollers (outlet roller) that can be heated to arbitrary temp, make the film forming resin combination of fusion to pass through on upper-lower interactive ground, promote crystallization (crystallization promotion operation) thus.Pass through from cooling roller then, thereby resin combination is solidified, make film.The temperature (resin temperature during the fusion film forming) that is melt into the resin combination in the membrane process is made as the surface temperature of the roller that is equivalent to the 4th roller 4 among Fig. 1.In addition, promoting the temperature of the resin combination in the operation about crystallization, be made as with the surface temperature of 3 outlet rollers 5 of Fig. 1 roughly the samely, is that crystallization promotes temperature with this temperature.Film forming speed is made as 5m/min, and the crystallization of essence promotes that the time (by the time of outlet roller) of operation is about 5 seconds.

Example I-2～I-5

Prepare resin combination in the compounding ratio shown in the following table 1,, make the film of example I-2～I-5 respectively by the operation same with example I-1.

Comparative Example I-1

Prepare resin combination in the compounding ratio shown in the following table 1,, make the film of Comparative Example I-1 by the operation same with example I-1.

By following method the rerum natura of the film that obtains in embodiment and the comparative example is measured, estimated.

＜melting temperature (Tm) (℃)＞

With by DSC(differential scanning calorimetry device) temperature during the summit of the endotherm(ic)peak of following fusion of resin combination that measure, after the film forming in temperature-rise period again is melting temperature (Tm) (Tm: be also referred to as crystal fusion peak temperature).

＜crystallized temperature (℃)＞

With the temperature of resin combination that measure by DSC, after the film forming when the summit of the exothermic peak of the accompanying crystallizationization in 200 ℃ temperature-fall period is crystallized temperature (Tc: be also referred to as the crystallization peak temperature).

＜film-forming properties result＞

(1) on roller, separates out fouling: by the dirt on visual valuation roller surface, do not have the state of dirt to be judged as " zero " (nothing) on the roller surface, have the state of dirt to be judged as " * " (having) on the roller surface.

(2) separability: estimate by the separability that the film forming resin combination of fusion is peeled off from the 4th roller 4 of Fig. 1, can be judged as " zero " (well) with the state of outlet roller 5 tractions, can't be judged as " * " (bad) with the state of outlet roller 5 tractions.

(3) pellicular front state: by visual observation gained film surface, the not coarse level and smooth state of film surface is judged as " zero " (well), will exist the calendering current mark (by the resin flow inequality cause concavo-convex), the state of coarse epidermis, pin hole is judged as " * " (bad).

During＜film forming the fusion of crystallization portion caloric receptivity Δ Hc ' (J/g)＞

Heat Δ Hc(J/g by the exothermic peak of the accompanying crystallizationization of film sample in temperature-rise period that measure by DSC, after the film forming) and the heat Δ Hm(J/g that follows fusion thereafter), use following formula (1) to calculate.

ΔHc′＝ΔHm-ΔHc （1）

The DSC and the condition determination that use in the mensuration of the fusion of crystallization portion caloric receptivity Δ Hc ' when melting temperature (Tm) (Tm), crystallized temperature (Tc) and film forming are as described below.

Device: SII NanoTechnology Inc. makes DSC6220

Condition:

Measure temperature field: 20 ℃ → 200 ℃ → 0 ℃ → 200 ℃ (promptly, at first carry out the mensuration from 20 ℃ to 200 ℃ temperature-rise period, then carry out the mensuration from 200 ℃ to 0 ℃ temperature-fall period, carry out the mensuration from 0 ℃ to 200 ℃ temperature-rise period more at last)

Intensification/cooling rate: 2 ℃/min

Measure atmosphere: under the nitrogen atmosphere (200ml/min)

Need to prove, in temperature-rise period again,, therefore judge crystallizable regional 100% crystallization under the heat-up rate of 2 ℃/min, the appropriate property of the calculating formula of the fusion of crystallization portion caloric receptivity when having confirmed film forming owing to there is not the exothermic peak of accompanying crystallizationization.

＜tear strength (N/mm)＞

Tear strength is that the paper-tear strength test method-Elmendorf type tear tester method according to JIS P8116 is measured.Employed determinator and condition determination are as described below.

Device: TESTER SANGYO CO .LTD. make Elmendorf type tear tester

Condition: specimen size: (films of overlapping 5 0.05mm) * width 76mm * length 63mm about thickness 0.25mm

Need to prove so that the direction parallel with length direction when being forming thin film travel direction (hereinafter referred to as the MD direction) and the mode of the direction (hereinafter referred to as TD direction) opposite with travel direction cut.

Tear strength calculation method: use following formula (2) to calculate.

T＝（A×p）/（n×t×1000）（2）

T: tear strength (N/mm)

A: the read value of scale (mN)

P: the overlapping number (being 16 in this device) of the test film of the benchmark of the scale of formation oscillator

N: the number of the test film of tearing simultaneously

T: the mean thickness of an average test film (mm)

＜swelling capacity＞

The sample (50mm * 50mm * thickness 0.05mm) of film or sheet is immersed in the solvent 15 minutes, and the solvent on the surface of the sample that takes out is removed with rag,, measure thus the weight of the weight behind the dipping before divided by dipping.

Wherein, employed solvent is 2 kinds of toluene and vinyl acetic monomers.

Whether qualifiedly judge: with below 2.0 as qualified.

＜initial elasticity modulus (MPa), breaking tenacity (MPa), elongation (%)＞

Test method according to plastics-tensile properties of JIS K7161 is measured.

The determinator and the condition determination that use are as follows.

Device: tensile testing machine (Autograph AG-20kNG, Shimadzu Seisakusho Ltd. makes)

Specimen size: thickness 0.05mm * width 10mm * length 100mm(wherein so that the mode of the travel direction (MD) of the direction parallel with length direction when being forming thin film is cut)

Condition determination:

Distance between chuck: 50mm

Draw speed: 300mm/min

＜thermal test＞

Cut into the two ends of the sample of thickness 0.05mm * width 200mm * length 300mm with the clip clamping, put in 100 ℃ the baking box 1 minute.Then, will when taking out, keep the sample of shape originally to be judged to be " zero " (well), and will not keep the sample of shape originally to be judged to be " * " (bad).

＜workability test＞

Use above-mentioned tensile testing machine, the sample that will cut into thickness 0.05mm * width 20mm * length 100mm is 25N/mm by stress ²Mode fix.Then, the central part between chuck is provided the otch of 1mm with razor by the mode that becomes the right angle with the MD direction.The sample that does not rupture at this moment is judged to be " zero " (well), the sample that ruptures is judged to be " * " (bad).The determinator and the condition determination that use are as described below.

Device: tensile testing machine (Autograph AG-20kNG, Shimadzu Seisakusho Ltd. makes)

Specimen size: thickness 0.05mm * width 20mm * length 100mm(wherein so that the mode of the travel direction (MD) of the direction parallel with length direction when being forming thin film is cut)

Condition determination:

Distance between chuck: 50mm

Draw speed: 50mm/min(is becoming 25N/mm ²The time stop)

The evaluation result of example I-1～I-5 and Comparative Example I-1 is shown in table 1.

From the evaluation result shown in the table 1 as can be known, the thermotolerance of the film of embodiments of the invention I-1～I-5 and processibility are all excellent.Relative therewith, the poor in processability of the film of Comparative Example I-1.

Table 1

Example II-1

Prepare resin combination in the compounding ratio shown in the following table 2, carry out melting mixing with Banbury mixer, rolling film forming to thickness with inverted L shape 4 roll calendars then becomes 50 μ m(and is melt into membrane process).Then, as shown in Figure 1, after being melt into membrane process, and then dispose 3 rollers (outlet roller) that can be heated to arbitrary temp, make the film forming resin combination of fusion to pass through on upper-lower interactive ground, promote crystallization (crystallization promotion operation) thus.Pass through from cooling roller then, thereby resin combination is solidified, make film (base material).The temperature (resin temperature during the fusion film forming) that is melt into the resin combination in the membrane process is made as the surface temperature of the roller that is equivalent to the 4th roller 4 among Fig. 1.In addition, promoting the temperature of the resin combination in the operation about crystallization, be made as with the surface temperature of 3 outlet rollers 5 of Fig. 1 roughly the samely, is that crystallization promotes temperature with this temperature.Film forming speed is made as 5m/min, and the crystallization of essence promotes that the time (by the time of outlet roller) of operation is about 5 seconds.

On the other hand, at 100 weight part thermoset add-on type organosilicons (trade(brand)name " KS-847T "), Shin-Etsu Chemial Co., Ltd makes, 30 weight % toluene solutions) in, add 1 weight part platinum catalyst (trade(brand)name " PL-50T ", Shin-Etsu Chemial Co., Ltd makes, toluene solution), 3000 weight part heptane, mixing, dissolving prepare remover combination.The mode that the thickness that (solidifies back) after going up with drying by the above-mentioned film that obtains (barrier film base material) becomes 0.2 μ m is coated with this remover combination of heat drying, thereby obtains barrier film.

Example II-2～II-5

Prepare resin combination in the compounding ratio shown in the following table 2, by with the same operation of example II-1 make respectively example II-2～II-5 film (the barrier film base material, and then, similarly carry out with example II-1 and obtain barrier film.

Comparative Example I I-1

Prepare resin combination in the compounding ratio shown in the following table 2, by making the film (base material) of Comparative Example I I-1 with the same operation of example II-1, and then, similarly carry out with example II-1 and obtain barrier film.

The physical property measurement of barrier film base material [melting temperature (Tm) (℃), crystallized temperature (℃), when film-forming properties result, film forming crystallization portion fusion caloric receptivity Δ Hc ' (J/g), tear strength (N/mm), swelling capacity, initial elasticity modulus (MPa), breaking tenacity (MPa), elongation (%)] by carrying out with aforementioned same method.

The evaluation of barrier film is undertaken by following method.

＜thermal test＞

Cut into the two ends of the barrier film sample of width 200mm * length 300mm with the clip clamping, put in 100 ℃ the baking box 1 minute.Then, will when taking out, keep the sample of shape originally to be judged to be " zero " (well), and will not keep the sample of shape originally to be judged to be " * " (bad).

＜workability test＞

Use above-mentioned tensile testing machine, the sample that will cut into thickness 0.05mm * width 20mm * length 100mm is 25N/mm by stress ²Mode fix.Then, the central part between chuck is provided the otch of 1mm with razor by the mode that becomes the right angle with the MD direction.The sample that does not rupture at this moment is judged to be " zero " (well), the sample that ruptures is judged to be " * " (bad).The determinator and the condition determination that use are as described below.

Device: tensile testing machine (Autograph AG-20kNG, Shimadzu Seisakusho Ltd. makes)

Specimen size: thickness 0.05mm * width 20mm * length 100mm(wherein so that the mode of the travel direction (MD) of the direction parallel with length direction when being forming thin film is cut)

Condition determination:

Distance between chuck: 50mm

Draw speed: 50mm/min(is reaching 25N/mm ²The time stop)

The evaluation result of example II-1～II-5 and Comparative Example I I-1 is shown in table 2.

From the evaluation result shown in the table 2 as can be known, the thermotolerance of the barrier film of embodiments of the invention II-1～II-5 and processibility are all excellent.Relative therewith, the poor in processability of the barrier film of Comparative Example I I-1.

Table 2

EXAMPLE III-1

Prepare resin combination in the compounding ratio shown in the following table 3, carry out melting mixing with Banbury mixer, rolling film forming to thickness with inverted L shape 4 roll calendars then becomes 50 μ m(and is melt into membrane process).Then, as shown in Figure 1, after being melt into membrane process, and then dispose 3 rollers (outlet roller) that can be heated to arbitrary temp, make the film forming resin combination of fusion to pass through on upper-lower interactive ground, promote crystallization (crystallization promotion operation) thus.Pass through from cooling roller then, thereby resin combination is solidified, make film (base material).The temperature (resin temperature during the fusion film forming) that is melt into the resin combination in the membrane process is made as the surface temperature of the roller that is equivalent to the 4th roller 4 among Fig. 1.In addition, promoting the temperature of the resin combination in the operation about crystallization, be considered as with the surface temperature of 3 outlet rollers 5 of Fig. 1 roughly the samely, is that crystallization promotes temperature with this temperature.Film forming speed is made as 5m/min, and the crystallization of essence promotes that the time (by the time of outlet roller) of operation is about 5 seconds.

On the other hand, acrylic acid polymer (the weight-average molecular weight: about 400,000) that forms by ethyl propenoate/2-EHA (60 weight parts/40 weight parts) at 100 weight parts, with 10 weight part rosin phenolic aldehyde is that tackifier and toluene mix equably, and dissolving prepares binder composition.Going up by the above-mentioned film that obtains (base material) with dried thickness is that the mode of 50 μ m is coated with dry this binder composition, thereby obtains adhesive sheet.

EXAMPLE III-2～III-5

Prepare resin combination in the compounding ratio shown in the following table 3, by making the film (base material) of EXAMPLE III-2～III-5 respectively with the same operation of EXAMPLE III-1, and then, similarly carry out with EXAMPLE III-1 and obtain adhesive sheet.

Comparative Example I II-1

Prepare resin combination in the compounding ratio shown in the following table 3, by similarly operating the film (base material) of making Comparative Example I II-1 with EXAMPLE III-1, and then, similarly carry out with EXAMPLE III-1 and obtain adhesive sheet.

The physical property measurement of base material [melting temperature (Tm) (℃), crystallized temperature (℃), when film-forming properties result, film forming crystallization portion fusion caloric receptivity Δ Hc ' (J/g), tear strength (N/mm), swelling capacity, initial elasticity modulus (MPa), breaking tenacity (MPa), elongation (%)] by carrying out with aforementioned same method.

The evaluation of adhesive sheet is undertaken by following method.

＜thermal test＞

Cut into the two ends of the adhesive sheet sample of width 200mm * length 300mm with the clip clamping, put in 100 ℃ the baking box 1 minute.Then, will when taking out, keep the sample of shape originally to be judged to be " zero " (well), and will not keep the sample of shape originally to be judged to be " * " (bad).

＜workability test＞

Use tensile testing machine, the sample that will cut into thickness 0.05mm * width 20mm * length 100mm is 25N/mm by stress ²Mode fix.Then, the central part between chuck is provided the otch of 1mm with razor by the mode that becomes the right angle with the MD direction.The sample that does not rupture at this moment is judged to be " zero " (well), the sample that ruptures is judged to be " * " (bad).The determinator and the condition determination that use are as described below.

Device: tensile testing machine (Autograph AG-20kNG, Shimadzu Seisakusho Ltd. makes)

Specimen size: thickness 0.05mm * width 20mm * length 100mm(wherein so that the mode of the travel direction (MD) of the direction parallel with length direction when being forming thin film is cut)

Condition determination:

Distance between chuck: 50mm

Draw speed: 50mm/min(is reaching 25N/mm ²The time stop)

The evaluation result of EXAMPLE III-1～III-5 and Comparative Example I II-1 is shown in table 3.

From the evaluation result shown in the table 3 as can be known, the thermotolerance of the adhesive sheet of embodiments of the invention III-1～III-5 and processibility are all excellent.Relative therewith, the poor in processability of the adhesive sheet of Comparative Example I II-1. Table 3

EXAMPLE IV-1

Prepare resin combination in the compounding ratio shown in the following table 4, carry out melting mixing with Banbury mixer, rolling film forming to thickness with inverted L shape 4 roll calendars then becomes 50 μ m(and is melt into membrane process).Then, as shown in Figure 1, after being melt into membrane process, and then dispose 3 rollers (outlet roller) that can be heated to arbitrary temp, make the film forming resin combination of fusion to pass through on upper-lower interactive ground, promote crystallization (crystallization promotion operation) thus.Pass through from cooling roller then, thereby resin combination is solidified, make film (base material).The temperature (resin temperature during the fusion film forming) that is melt into the resin combination in the membrane process is made as the surface temperature of the roller that is equivalent to the 4th roller 4 among Fig. 1.In addition, promoting the temperature of the resin combination in the operation about crystallization, be made as with the surface temperature of 3 outlet rollers 5 of Fig. 1 roughly the samely, is that crystallization promotes temperature with this temperature.Film forming speed is made as 5m/min, and the crystallization of essence promotes that the time (by the time of outlet roller) of operation is about 5 seconds.

On the other hand; in the acrylic acid polymer (weight-average molecular weight: in the 20 weight % toluene solutions 400,000) that forms by 2-EHA/N-acryloyl morpholine/vinylformic acid (70 weight parts/30 weight parts/3 part); with respect to 100 parts by weight of acrylic acid based polymers; compounding 2 weight part epoxies are linking agent (trade(brand)name " TETRAD C "; MITSUBISHI GAS CHEMICAL COMPANY; INC. manufacturing), 2 weight part isocyanate-based linking agents (trade(brand)name " CORONATE L ", Japanese polyurethane Co., Ltd. makes) prepare binder composition.Going up by the above-mentioned film that obtains (base material) with dried thickness is that the mode of 5 μ m is coated with dry this binder composition film that is protected.

EXAMPLE IV-2～IV-5

Prepare resin combination in the compounding ratio shown in the following table 4, by similarly operating the film (base material) of making EXAMPLE IV-2～IV-5 respectively with EXAMPLE IV-1, and then, similarly carry out and the film that is protected with EXAMPLE IV-1.

Comparative Example I V-1

Prepare resin combination in the compounding ratio shown in the following table 4, by similarly operating the film (base material) of making Comparative Example I V-1 with EXAMPLE IV-1, and then, similarly carry out and the film that is protected with EXAMPLE IV-1.

The physical property measurement of base material [melting temperature (Tm) (℃), crystallized temperature (℃), when film-forming properties result, film forming crystallization portion fusion caloric receptivity Δ Hc ' (J/g), tear strength (N/mm), swelling capacity, initial elasticity modulus (MPa), breaking tenacity (MPa), elongation (%)] by carrying out with aforementioned same method.

The evaluation of protective film is undertaken by following method.

＜thermal test＞

Cut into the two ends of the protective film sample of width 200mm * length 300mm with the clip clamping, put in 100 ℃ the baking box 1 minute.Then, will when taking out, keep the sample of shape originally to be judged to be " zero " (well), and will not keep the sample of shape originally to be judged to be " * " (bad).

＜workability test＞

Use above-mentioned tensile testing machine, the sample that will cut into thickness 0.05mm * width 20mm * length 100mm is 25N/mm by stress ²Mode fix.Then, the central part between chuck is provided the otch of 1mm with razor by the mode that becomes the right angle with the MD direction.The sample that does not rupture at this moment is judged to be " zero " (well), the sample that ruptures is judged to be " * " (bad).The determinator and the condition determination that use are as described below.

Device: tensile testing machine (Autograph AG-20kNG, Shimadzu Seisakusho Ltd. makes)

Specimen size: thickness 0.05mm * width 20mm * length 100mm(wherein so that the mode of the travel direction (MD) of the direction parallel with length direction when being forming thin film is cut)

Condition determination:

Distance between chuck: 50mm

Draw speed: 50mm/min(is reaching 25N/mm ²The time stop)

The evaluation result of EXAMPLE IV-1～IV-5 and Comparative Example I V-1 is shown in table 4.

From the evaluation result shown in the table 4 as can be known, the present invention the thermotolerance of protective film and the processibility of EXAMPLE IV-1～IV-5 all excellent.Relative therewith, the poor in processability of the protective film of Comparative Example I V-1.

Table 4

Utilizability on the industry

According to poly lactic acid series film of the present invention or sheet, has following characteristic: even surpassing under 100 ℃ the high temperature, film or sheet can not fuse yet, be out of shape, in addition, keep the rigidity that originally has, and when the manufacturing of film or sheet, the man-hour of adding, when film or sheet are wound into the roller shape etc., even apply tension force, can not produce fracture, cracking yet.The base material of the barrier film that therefore, for example can be used as the base material of self adhesive tape or sheet, uses in self adhesive tape or sheet etc., the base material of protective film wait and utilize.

Description of reference numerals

1 the 1st roller

2 the 2nd rollers

3 the 3rd rollers

4 the 4th rollers

5 outlet rollers

6 cooling rollers

7 cooling rollers

8 resin combinations

9 spacer gels (resin is deposited glue)

10 forcing machine leading sections

Claims (10)

1. poly lactic acid series film or sheet is characterized in that, it is for containing the resin film or the sheet of poly(lactic acid) (A), and the fusion caloric receptivity Δ Hc ' of crystallization portion is more than the 10J/g during its film forming of trying to achieve by following formula (1),

ΔHc′＝ΔHm-ΔHc （1）

In the formula, Δ Hc is accompanied by the thermal discharge (J/g) of crystallization for film that measure by DSC, after the film forming or sheet at temperature-rise period, and Δ Hm is the caloric receptivity (J/g) that is accompanied by fusion thereafter,

And tear strength is that MD direction, width are that the TD direction is more than the 2.5N/mm at travel direction, and described tear strength is according to JIS P8116 paper-tear strength test method-Elmendorf type tear tester method.

2. poly lactic acid series film according to claim 1 or sheet, it further contains 0.5～15 weight part fluorine based polymer (B) with respect to 100 weight part poly(lactic acid) (A).

3. poly lactic acid series film according to claim 2 or sheet, wherein, fluorine based polymer (B) is the tetrafluoroethylene based polymer.

4. according to each described poly lactic acid series film or sheet in the claim 1～3, it further contains 0.1～15 weight part crystallization promoter (C) with respect to 100 weight part poly(lactic acid) (A).

5. according to each described poly lactic acid series film or sheet in the claim 1～4, it further contains 0.1～10 weight part acidic functionality modified olefin based polymer (D) with respect to 100 weight part poly(lactic acid) (A), and the acid value of described acidic functionality modified olefin based polymer (D) is that 10～70mgKOH/g, weight-average molecular weight are 10000～80000.

6. according to each described poly lactic acid series film or sheet in the claim 1～5, it is for by being melt into film or the sheet that the embrane method film forming obtains.

7. poly lactic acid series film according to claim 6 or sheet, wherein, being melt into embrane method is rolling process.

8. a barrier film is characterized in that, it is for there being the barrier film of stripper processing layer at least one mask of barrier film base material, and this barrier film base material is to be made of each described poly lactic acid series film or sheet in the claim 1～7.

9. self adhesive tape or sheet is characterized in that, it is for having the self adhesive tape or the sheet of binder layer at least one mask of base material, and this base material is to be made of each described poly lactic acid series film or sheet in the claim 1～7.

10. a protective film is characterized in that, it is for there being the protective film of releasable binder layer at least one mask of base material, and this base material is to be made of each described poly lactic acid series film or sheet in the claim 1～7.

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