CN102369235B - Polypropylene resin film for surface protection, and surface protective film - Google Patents

Polypropylene resin film for surface protection, and surface protective film Download PDF

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Publication number
CN102369235B
CN102369235B CN201080014351.8A CN201080014351A CN102369235B CN 102369235 B CN102369235 B CN 102369235B CN 201080014351 A CN201080014351 A CN 201080014351A CN 102369235 B CN102369235 B CN 102369235B
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film
polypropylene resin
surface protection
resin film
antioxidant
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CN102369235A (en
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江崎浩明
西忠嗣
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Toyobo Co Ltd
Toyo Textile Co Ltd
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Toyo Textile Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/306—Applications of adhesives in processes or use of adhesives in the form of films or foils for protecting painted surfaces, e.g. of cars
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/006—Presence of polyolefin in the substrate

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Materials Engineering (AREA)

Abstract

Disclosed is a polypropylene resin film for surface protection, which has excellent thermal dimensional stability, planarity, impact resistance and bonding workability, while being reduced in fish eyes. The polypropylene resin film for surface protection is free from wrinkles or sags when the film is rolled into a roll. The polypropylene resin film is suitable, for example, for a base film of a protective film. Also disclosed is a protective film which is obtained by providing the polypropylene resin film for surface protection with an adhesive layer. Specifically disclosed is a polypropylene resin film for surface protection, which is substantially composed of a polypropylene resin and is characterized by having a xylene-soluble content at 20 DEG C of more than 9% but less than 15%, a crystal nucleator content of not more than 100 ppm, a film thickness variation in the width direction of not less than 1% but not more than 10%, a coefficient of kinetic friction of not more than 1.0, and a tensile modulus of elasticity of not less than 500 MPa but not more than 900 MPa.

Description

Polypropylene resin film and surface protection film for surface protection
Technical field
The present invention relates to surface protection polypropylene resin film and surface protection film; few and then the white point (fish eye) of flexibility of operation the dividing a word with a hyphen at the end of a line property good and additive such as the thermal distortion patience while specifically, relating to high temperature and planarity is high, such as bonding processing less, in the surface protection purposes of various uses, particularly various article applicable surface protection with polypropylene resin film and use the surface protection film of this surface protection polypropylene resin film.
Background technology
Polypropylene-base unstretching film is because the transparency is good and cheap, is therefore widely used as various wrapping material such as food product pack and taking the surface protection of various article as the base material of the surface protection film of object.
And then; the surface protection film of protecting as the film of precise electronic goods, parts and associated components for to associated materials such as metal sheet, decorative sheet, resin board, sheet glass etc., liquid crystal panel or polaroid etc., automobile uses, or as the resist film of the splicing ear portion for the protection of for plating flexible print wiring board partly etc. or the surface protection film of etching block film (エ Star チ Application グ resist film), protect the surperficial surface protection film use of semiconductor element by stacked film on the face that there is no circuit of semiconductor element.
In recent years, along with the expansion of purposes, more and more strengthen for the requirement of quality and cost, and demand is except the laminating flexibility of operation to protected body, also good surface protection film of the ease of processing of tackiness agent.
Especially, in order to improve process velocity of bonding processing etc. and constantly carry out the high temperature of processing temperature, and, even if require at high temperature to process tackiness agent, the thermal distortion that caused by this processing temperature is also little and add the dimensional stability good (being also sometimes only called heat-resisting dimensional stability) in man-hour.
About polypropylene film, several technology (for example, with reference to patent documentation 1～4) that above-mentioned heat-resisting dimensional stability is improved are disclosed.
But the rigidity of disclosed heat sealability polypropylene screen is insufficient in patent documentation 1, in patent documentation 2, disclosed transparent polypropylene sheet is difficult to laminating.
In addition, the surface protection of recording in patent documentation 3 and patent documentation 4 is also that rigidity is large, laminating flexibility of operation is poor with polypropylene screen.
In addition, while film being wound into roller shape, exist and easily produce fold and lax problem.
In addition, in the time of coating adhesive, there is the problem of film distortion.
Prior art document
Patent documentation:
Patent documentation 1: Japanese kokai publication hei 09-12657 communique
Patent documentation 2: TOHKEMY 2003-170485 communique
Patent documentation 3:WO2006/057294
Patent documentation 4: TOHKEMY 2007-270005 communique
Summary of the invention
Invent problem to be solved
When the invention provides that heat-resisting dimensional stability and planarity are good, shock-resistance and laminating excellent processability, white point are few and then are wound into roller shape, do not produce fold and lax, for example, as the applicable surface protection polypropylene resin film of the base material film of protective membrane and at the protective membrane that bonding coat is set on polypropylene resin film forms for this surface protection.
For the means of dealing with problems
The inventor, in order to solve above-mentioned problem, conducts in-depth research repeatedly, and result has completed the present invention.
; the present invention is a kind of surface protection polypropylene resin film; it is characterized in that; in fact taking polypropylene-based resin as principal constituent; 20 DEG C of xylene soluble part amounts exceed 9% and lower than 16%, the containing ratio of nucleating agent is below 100ppm, and the thickness variation rate of the width of film is more than 1% and below 10%; kinetic friction coefficient is below 1.0, and modulus in tension is more than 500MPa and below 900MPa.
In this situation, the content of the anti blocking agent in preferred film is below 50ppm, and resistance to adhesive is below 10mN.
In addition, in this situation, the maximum diameter in preferred film is that white point more than 0.2mm is 0/m 2, and the white point that maximum diameter is less than 0.2mm is 100/m 2below.
In addition, in this situation, the longitudinal Young's modulus at 23 DEG C of preferred film is more than 500Mpa.
In addition, in this situation, the shock strength at 23 DEG C of preferred film is more than 0.3J.
In addition, in this situation, preferably at least contain esters of acrylic acid antioxidant, and contain at least one antioxidant being selected from Phosphorus antioxidant and phenol antioxidant.
In addition, in this situation, the amplitude of fluctuation of 20 DEG C of xylene soluble part amounts of preferred above-mentioned film is lower than 2%.
In addition, the present invention arranges the surface protection film that binder layer forms at least one side of above-mentioned surface protection polypropylene resin film.
Invention effect
The present invention has heat-resisting dimensional stability and planarity is good, shock-resistance and laminating processibility and do not produce fold when preventing that albefaction effect is good, white point is few and then being wound into roller shape and lax and for example as the applicable effect of the base material film of protective membrane.
Surface protection of the present invention uses polypropylene resin film due to heat-resisting excellent size stability; therefore; even if the processing such as the secondary processing adaptability of such as bonding processing etc. is good, be particularly dried under near the high temperature 130 DEG C also can suppress the generation that hot fold and film are lax; therefore, can improve this secondary processing productivity, suppress the generation by the lax defective products causing of hot fold and film.
In addition, polypropylene resin film of the present invention does not preferably contain in fact anti blocking agent, the problem coming off that for example can avoid in the time that the film that makes to contain anti blocking agent moves causing by wearing and tearing etc. anti blocking agent, therefore, suppresses the pollution and the obstacle generation etc. that are caused by this cast.
In addition, although the present invention does not contain in fact lubricant and anti blocking agent, because surfaceness is suitable, the oilness of film and resistance to adhesive are good, and rigidity is good, and therefore, the treatability of film is good.
In addition, because the transparency is good, therefore the visibility of protected body is good.
In addition, owing to having film strength, therefore, treatability is good.
In addition, although above-mentioned heat-resisting dimensional stability improves, shock strength is good, keeps by form the formedness of the shock-resistance of giving with block polypropylene resinoid, and the reliability while use as protective membrane is high.
Embodiment
Polypropylene resin film of the present invention is taking polypropylene-based resin as principal constituent, preferably contain polypropylene-based resin 70 % by weight in film more than, more than further preferably containing 80 % by weight.
The polypropylene-based resin using in the present invention, can be by will be from sym-propene polymer resin, the atactic copolymerized polypropene resin that copolymerization has ethene, other alpha-olefins to form, and the one to three of selecting in block copolymerization polypropylene resin kind of a mixing is used.
From transparent viewpoint, the preferably main atactic copolymerized polypropene resin that uses sym-propene polymer resin or copolymerization to have ethene, other alpha-olefins to form, the preferred main block copolymerization polypropylene resin that uses making impact and oilness, particularly resistance to adhesive improves in the situation that.Ratio of mixture can regulate arbitrarily.
About the composition of above-mentioned polypropylene-based resin, there is no particular limitation, atactic copolymerized polypropene resin if, and, from the viewpoint of heat-resisting dimensional stability, alpha-olefin content is preferably below 5%.In addition, block copolymerization polypropylene resin if,, from the aspect of heat-resisting dimensional stability and oilness, resistance to adhesive, preferably its 20 DEG C of xylene soluble part amounts are 3～50%, more preferably 5～30% scope.
The limiting viscosity of preferred above-mentioned polypropylene-based resin entirety is that the limiting viscosity of 1.5～4.0,20 DEG C of xylene soluble parts is that the limiting viscosity of 1.0～4.0,20 DEG C of insoluble parts of dimethylbenzene is 1.0～4.0.The melt flow rate (MFR) of the polypropylene-based resin using in the present invention in addition, is preferably 2～20g/10 minute at 230 DEG C.
As the alpha-olefin random copolymers elastomerics using in the present invention, can use ethylene-propylene, ethene-butylene or propene-1-butene two metaclass, ethylene-propylene-butylene ternary analog copolymer or their mixture.In addition, not damaging in the scope of its characteristic, the multipolymer that can also use copolymerization to have other monomer to form.Particularly preferably use above-mentioned binary analog copolymer.In addition, from giving to duplexer the viewpoint of preferred elastic force, preferably using dimension card (PVC ガ Star ト) softening temperature is below 60 DEG C and surface hardness is 80 ° of following multipolymers.
In the present invention, from the viewpoint of thermotolerance and oilness, particularly preferably contain block copolymerization polypropylene resin.
In addition, according to various objects, can add other a small amount of alpha-olefin random copolymerization elastomericss, ionomer, other masterbatch classes.
Polypropylene resin film of the present invention need to make 20 DEG C of xylene soluble part amounts exceed 9% and lower than 16%.
Below 9%, easily there is viscous deformation in film in the time of high temperature process if, the laminating adaptability of film and prevent albefaction weak effect.
More than 16%, film easily extends if, and adhesive coated flexibility of operation is poor, therefore not preferred.
The lower limit of other 20 DEG C of xylene soluble part amounts, the viewpoint of the albefaction when preventing that film is bending, more preferably more than 10%, in addition, from the aspect of the resistance to blocking characteristics of film, more preferably below 14%.
In the present invention, as mentioned above, preferably do not carry out the lubricant implemented and the cooperation of anti blocking agent in common polypropylene resin film, in this situation, need to suppress oilness, adhesive deteriorated of film.The film protrusion of surface that sea/island structure that this correspondence preferably according to above-mentioned resin composition, is particularly produced by block copolymerized resin, vinyl copolymer elastomer causes is carried out.
Now, as the lubricating property of film of the present invention, in aftermentioned evaluation, needing kinetic friction coefficient is below 1.0.In addition, more preferably, below 0.9, most preferably be below 0.8.
If kinetic friction coefficient, outside this scope, while film being wound into roller shape, while getting rid of the air between film, easily produces the adhesion between film, produce fold and a lax major cause thereby become.
In addition, as the resistance to blocking characteristics of film of the present invention, in aftermentioned is evaluated, be preferably below 1～10mN.More preferably below 1～7mN.
On the other hand, sea/the island structure being produced by this block copolymerized resin and forming of the film protrusion of surface that causes causes the reduction of the film transparency, therefore, in the method, the oilness of being brought by forming of protrusion of surface and resistance to adhesive improve effect and the transparency guarantee to become antinomy phenomenon.Therefore, the haze value of film becomes important factor.
Therefore,, in the present invention, the haze value that makes film is below 40%, to become very important.Preferably below 35%, more preferably below 30%.Be below 40% by making haze value, the visibility of packed article and protected body improves, and in the situation that using as bag material, easily confirms the content of packed article.In addition, in the situation that using materials'use as surface protection film, under the state of coating surface protective membrane, for example, can carry out the inspection of protected body etc.On the contrary, in the situation that haze value exceedes 40%, transparent variation, the visibility of packed article and protected body reduces, therefore not preferred.On the other hand, although because the lower limit of haze value is when lower, the transparency is higher and preferred haze value is low, and giving by aforesaid method in the association of viewpoint of oilness, preferably haze value is more than 5%, more preferably more than 10%.
In addition, surface protection polypropylene resin film of the present invention, the content of the anti blocking agents such as the inorganic and/or organic particulate in preferred film is below 50ppm.The content of anti blocking agent is more preferably below 10ppm, particularly preferably in being below detectability in the common quantivative approach such as ash content or ultimate analysis., preferably do not contain in fact anti blocking agent.At this, the situation that does not contain in fact anti blocking agent and above-mentioned lubricant is identical meanings.According to this correspondence, coming off of the anti blocking agent that inhibition is caused by the wearing and tearing of the film in manufacture and the secondary processing operation of film, therefore, suppresses the pollution and the obstacle generation etc. that are caused by this cast.
For surface protection polypropylene resin film of the present invention, making the content of the lubricants such as polyethylene wax in film, calcium stearate, erucicamide, the two erucicamides of ethylene is that 50ppm is very important below.The content of lubricant is more preferably below 10ppm, particularly preferably in being below detectability in the common quantivative approach such as ultimate analysis and extraction method., preferably do not contain in fact lubricant.At this, do not contain in fact lubricant, do not refer to and actively add lubricant and masking.Why having above-mentioned scope is because have even without positive interpolation lubricant, and in the time that stock polymer and film are manufactured, due to commodity replacing etc. and the situation that lubricant trace is sneaked into, above-mentioned scope is not contain lubricant preferred embodiment in fact.By this correspondence, be suppressed at this lubricant of causing in the method that the oilness that coordinates this lubricant to make film improves to the migration on film surface and continue to occur the pollution of the protected body producing to the movement of protected body, thereby keep the limpid degree of protected body.
In the present invention, modulus in tension need to be more than 500MPa and below 900MPa.
If modulus in tension is too small, while film being wound into roller shape, film distortion, its result, residual stress on roller, produces fold and lax, thereby becomes problem.If contrary modulus in tension is excessive, the laminating of the film after adhesive coated becomes difficulty.
Surface protection polypropylene resin film of the present invention, the degree of crystallinity of the film preferably recording according to aftermentioned measuring method is 34～65%.When degree of crystallinity is less than 34%, be difficult to show heat-resisting dimensional stability, easily produce the lax of film and extend the man-hour that adds after enforcement in operation, and therefore, it is bad that planarity becomes, thereby not preferred.On the other hand, degree of crystallinity exceedes in 65% situation, and the remarkable variation of the transparency of film is therefore not preferred.In addition, in the situation that degree of crystallinity exceedes 65%, Young's modulus increases, laminating flexibility of operation variation.
The lower limit of the degree of crystallinity of film more preferably more than 40%, from the viewpoint of heat-resisting dimensional stability, most preferably is more than 50%.On the other hand, from transparent viewpoint, the upper limit of the degree of crystallinity of film is preferably below 60%.
In addition, even if surface protection of the present invention can be for not containing in fact nucleating agent with polypropylene resin film, also reach the polypropylene resin film of desired degree of crystallinity (34～65%) according to manufacture method.As manufacture method, chill-roll temperature high temperature that can be when making molten resin traction, cooling curing or complete by thermal treatment (annealing).
Surface protection polypropylene resin film of the present invention, if the scope of nucleating agent below 100ppm can be added.By adding nucleating agent, can improve the heat-resisting dimensional stability of film.On the other hand, when interpolation nucleating agent exceedes 100ppm, can determine according to the condition that melt extrudes of resin, but the tendency that exists the white point in film to increase produces the situation that becomes problem.And, add nucleating agent while exceeding 100ppm, be likely produced as the impurity of removing in resin and the filter stoppage possessing and cause boosting etc. and make the problems such as productivity reduction in forcing machine, therefore not preferred.
This nucleating agent does not limit, and can enumerate: taking the metal-salt of rosin based as the nucleating agent of principal constituent, nucleating agent and the nucleating agent being made up of aromatic series organophosphate metal-salt etc. of sorbose alcohols.
In addition, for surface protection of the present invention the preferred degree of birefringence of polypropylene resin film (△ is n) 0.4 × 10 -3～2.5 × 10 -3.Exceed 2.5 × 10 in degree of birefringence -3situation under, it is excessive that anisotropy becomes, and easily becomes fold and lax major cause.
On the other hand, degree of birefringence is lower than 0.4 × 10 -3time, the elongation that easily produces film, therefore, it is bad that planarity becomes, and heat-resisting dimensional stability variation is therefore not preferred.From keeping the viewpoint of heat-resisting dimensional stability and planarity, the degree of birefringence of film is preferably 0.6 × 10 -3above, in addition more preferably 0.8 × 10 -3above.On the other hand, from preventing the fold of film and lax viewpoint, the degree of birefringence of film is preferably 2.3 × 10 -3below, in addition more preferably 2.2 × 10 -3below.
In the present invention, surface protection polypropylene resin film of the present invention, the shock strength at 23 DEG C of preferred film is more than 0.3J.More preferably more than 0.5J.Conventionally, while improving above-mentioned rigidity and heat-resisting dimensional stability, shock strength has the tendency being lowered.When this shock strength reduces, the reliability of the shock-resistance when using in situation about using as packing bag or protective membrane etc. reduces, and therefore, preferably gives on the basis of above-mentioned characteristic and meets this characteristic.Based on the balance of other characteristics, the upper limit is preferably about 0.8J.
The method of giving above-mentioned shock strength does not limit, but is subject to the impact of above-mentioned ethylene content large.Preferably realize as the net effect of the preferred implementation recorded in this specification sheets that comprises described ethylene content.
In the present invention, surface protection polypropylene resin film of the present invention, the maximum diameter in preferred film is that white point more than 0.2mm is 0/m 2.The white point that further preferred maximum diameter is less than 0.2mm is 100/m 2below.Most preferably to be less than the white point of 0.2mm be also 0/m to maximum diameter 2below, but according to the requirement degree in economy and market etc., preferred above-mentioned scope.More preferably 2～80/m 2below, 2～60/m more preferably 2below.The minimum diameter of the white point that can visually judge in addition, is 0.03～0.05mm.By this correspondence, the obstacle generation that the plating solution being produced by above-mentioned Poor cohesion when can suppressing bad order and for example using as the base material film of protective membrane causes to soaking into of protection part etc.
The method that realizes above-mentioned characteristic does not limit, as described later, and the most applicable cooperation of carrying out antioxidant sometimes.
Esters of acrylic acid antioxidant of the present invention, be have in molecule, comprise acrylate residue amphyl antioxidant.As acrylic compound, for example can enumerate: 2,4-bis-tert-pentyls-6-[1-(3,5-bis-tert-pentyls-2-hydroxy phenyl) ethyl] phenyl acrylate, 2,4-bis-tert-pentyls-6-[1-(3,5-bis-tert-pentyls-2-hydroxy phenyl) butyl] phenyl acrylate, 2,4-bis-tert-pentyls-6-[1-(3,5-, bis-tert-pentyls-2-hydroxy phenyl) propyl group] phenyl acrylate, the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate etc.
Be preferably 2,4-, bis-tert-pentyls-6-[1-(3,5-, bis-tert-pentyls-2-hydroxy phenyl) ethyl] phenyl acrylate and the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate.
As aforesaid propylene ester compound, can be from commercially available acrylic compound suitable choice for use.For example can enumerate: ス ミ ラ イ ザ mono-GM (registered trademark) that manufactures as the Sumitomo Chemical Co of the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, as 2,4-bis-tert-pentyls-6-[1-(3,5-, bis-tert-pentyls-2-hydroxy phenyl) ethyl] ス ミ ラ イ ザ mono-GS (registered trademark) etc. that manufactures of the Sumitomo Chemical Co of phenyl acrylate.Particularly preferably use ス ミ ラ イ ザ mono-GS (registered trademark).
The use level of the aforesaid propylene esters of gallic acid antioxidant in the present invention does not limit, and is preferably the scope of 100～1000ppm with respect to above-mentioned all polypropylene-based resin compositions.More preferably 200～800ppm, more preferably 300～700ppm.In the situation that exceeding 1000ppm, in film making process, the pollution of cooling roller increases, therefore not preferred.It is distinctive light yellow that film is also dyed to antioxidant, therefore not preferred.On the contrary, in the time being less than 100ppm, combined effect described later reduces, therefore not preferred.Preferably only the upper limit of the antioxidant use level of the upper limit of the use level of aforesaid propylene esters of gallic acid antioxidant than 2 kinds described later is low, this supposition be due to, this esters of acrylic acid antioxidant is compared with other antioxidants, solvability for the rubber constituent of polypropylene-based resin is high, therefore be assigned to more in the rubber constituent in film, and this rubber constituent part is compared with base resin, crystallization speed by cooling roller is slower, in situation about therefore contacting with cooling roller, the aforesaid propylene esters of gallic acid antioxidant being assigned in this rubber constituent easily moves to cooling roller, therefore improve the dustiness of cooling roller.Above-mentioned be for example in above-mentioned patent documentation 23 grades, in the masking of disclosed use sym-propene polymer resin, do not have produce but in the present invention produce endemism.
As the concrete example of above-mentioned Phosphorus antioxidant, for example, can enumerate: the thermo-stabilizer that contains the phosphorus atom of 3 valencys and this phosphorus atom in molecule and have at least one P-O-C key.For example can enumerate: tributyl phosphorous acid ester, trioctylphosphine phosphorous acid ester, three lauryl phosphorous acid esters, three stearyl phosphorous acid esters, tridecyl phosphorous acid ester, trimethylphenyl phosphorous acid ester, thricyclohexyl phosphorous acid ester, triphenyl phosphorous acid ester, three lauryl thiophosphites, three (2-ethylhexyl) phosphorous acid ester, three (isodecyl) phosphorous acid ester, three (tridecyl) phosphorous acid ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, three (butoxyethyl group) phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, three (3,5-di-tert-butyl-hydroxy phenyl) phosphorous acid ester, three [4,4 '-isopropylidene two (2-TBP)] phosphorous acid ester, three (1,3-distearyl acyl-oxygen base sec.-propyl) phosphorous acid ester, 2-ethylhexyl phenylbenzene phosphorous acid ester, decyl phenylbenzene phosphorous acid ester, phenyl two 2-ethylhexyl phosphorous acid esters, phenyl didecyl phosphorous acid ester, phenyl diiso decyl phosphorous acid ester, phenyl two (tridecyl) phosphorous acid ester, phenylbenzene nonyl phosphorous acid ester, phenylbenzene iso-octyl phosphorous acid ester, phenylbenzene isodecyl phosphorous acid ester, phenylbenzene list (tridecyl) phosphorous acid ester, dibutyl H-Phosphonate, 4,4 '-isopropylidene biphenol alkyl (C12～C15) phosphorous acid ester, 4, two (the 3-methyl-6-tert butyl phenyl) two-tridecyl phosphorous acid esters of 4 '-butylidene, 2,2-methylene-bis (4,6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, 2,2 '-ethylenebis (4,6-DI-tert-butylphenol compounds) fluorophosphite, two (2,4-di-t-butyl-6-aminomethyl phenyl) ethide phosphite ester, 4, two (2-TBP) two (nonyl phenyl) phosphorous acid esters of 4 '-isopropylidene, distearyl pentaerythrityl diphosphite, two (nonyl phenyl) pentaerythritol diphosphites, diphenyl pentaerythritol diphosphites, phenyl 4,4 '-isopropylidene biphenol pentaerythritol diphosphites, two (4,6-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, phenyl-dihydroxyphenyl propane pentaerythritol diphosphites, tetraphenyl dipropylene glycol diphosphites, four (tridecyl)-1,1,3-tri-(2-methyl-5-tert-butyl-hydroxy phenyl) butane diphosphites, four (C12～C15 mixed alkyls)-4,4 '-isopropylidene phenylbenzene diphosphites, four (tridecyl)-4, two (3 methy 6 tert butyl phenol) diphosphites of 4 '-Ding fork, four (4,6-di-tert-butyl-phenyls)-4,4 '-biphenylene, two phosphinates, four (2-methyl-4,6-di-tert-butyl-phenyls)-4,4 '-biphenylene, two phosphinates, two (octyl phenyls) two [4,4 '-Ding fork two (3 methy 6 tert butyl phenol)] 1,6-hexane diol diphosphites, hydrogenation-4,4 '-isopropylidene biphenol is gathered phosphorous acid ester, mix-9-oxa--10-phospho hetero phenanthrene-10-oxide compound of 9,10-dihydro-9-oxy, 2-[{2,4,8, 10-tetra-(1,1-dimethyl ethyl) dibenzo (D, F) (1, 3,2)-dioxa phosphine-6-yl } oxygen base]-N, the two (2-[{2 of N-, 4,8,10-tetra-(1, 1-dimethyl ethyl) dibenzo (D, F) (1,3,2)-dioxa phosphine-6-yl } oxygen base] ethyl) ethamine, 1,1,3-tri-(2-methyl-4-bis--tridecyl phosphorous acid ester-5-tert-butyl-phenyl) butane, 3,4,5,6-, tetra-phendioxins, 2-oxa-phosphine-2-oxide compound etc.
Preferably do not there is the compound of tetramethylolmethane skeleton: three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, three (3,5-di-tert-butyl-hydroxy phenyl) phosphorous acid ester, two (2,4-di-t-butyl-6-aminomethyl phenyl) ethide phosphite ester, four (2-methyl-4,6-di-tert-butyl-phenyl)-4,4 '-biphenylene, two phosphinates.
As the Phosphorus antioxidant using in the present invention, also can use commercially available product, for example, can enumerate: イ Le ガ Off is just ス 38 (Ciba company system), GSY-P101 (lucky rich Off ア イ Application ケ ミ カ Le company system), ウ Le ト ラ ノ Star Network ス 641 (ジ mono-イ mono-ス ペ ジ ヤ Le テ イ ケ ミ カ Le ズ company system) etc. of ス 168 (Ciba company system), イ Le ガ Off.
The use level of the above-mentioned Phosphorus antioxidant in the present invention does not limit, and is preferably the scope of 500～5000ppm with respect to above-mentioned whole polypropylene-based resin compositions.More preferably 1000～4000ppm, more preferably 1500～3000ppm.During lower than 500ppm, and reduce by the effect of aftermentioned antioxidant, therefore not preferred.On the contrary, in the situation that exceeding 5000ppm, and saturated by the effect of aftermentioned antioxidant, cause the pollution of the cooling roller in film albefaction and the film making process producing to the movement on film surface due to this antioxidant etc., therefore not preferred.
The phenol antioxidant using in the present invention for having the antioxidant of phenol derivatives in molecule, for example, can be enumerated: 2,6 di tert butyl 4 methyl phenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-, bis-tert-pentyls-4-methylphenol, tertiary octyl group-the 4-of 2,6-bis-n-propyl phenol, 2,6-dicyclohexyl-4-n-octyl phenol, 2-isopropyl-4-methyl-6-tert.-butyl phenol, the 2-tertiary butyl-2-ethyl-6-tert-octyl phenol, the tertiary hexylphenol of 2-isobutyl--4-ethyl-6-, 2-cyclohexyl-4-normal-butyl-6-isopropyl-phenol, dl-alpha-tocopherol, tertiary butylated hydroquinone, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2-thiobis (4-methyl-6-tert-butylphenol), 4,4 '-methylene-bis (2,6 di t butyl phenol), 2,2 '-methylene-bis [6-(1-methylcyclohexyl)-p-cresol], 2,2 '-ethylenebis (4,6-DI-tert-butylphenol compounds), 2,2 '-Ding fork two (2-tert-butyl-4-methyl-Phenol), the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, 2-[1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl]-4,6-di-tert-pentyl-phenyl acrylate, 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, triethylene glycol-bis-[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester], 1,6-hexane diol-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], 2,2-sulfo-divinyl two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester-diethyl ester, three (2,6-dimethyl-3-hydroxyl-4-tertiary butyl benzyl) isocyanuric acid ester, three (3,5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, three [(3,5-di-tert-butyl-hydroxy phenyl) propionyl oxygen base ethyl] isocyanuric acid ester, three (the 4-tertiary butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanuric acid ester, two (n-octyl sulfo-)-6-(4-hydroxyl-3,5-di-tert-butyl the amido)-1,3,5-triazines of 2,4-, four [methylene radical-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] methane, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol) terephthalate, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, 3,9-pair [1,1-dimethyl-2-{ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl oxygen base } ethyl]-2,4,8,10-tetra-oxaspiros [5,5] undecane, two [4-(2-(3, the 5-di-t-butyl-4-hydroxyl hydrogen cinnamoyloxy group)) ethoxyl phenenyl] propane of 2,2-, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl etc.
Be preferably β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl ester, four [methylene radical-3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane, three (3, 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, dl-alpha-tocopherol, three (2, 6-dimethyl-3-hydroxyl-4-tertiary butyl benzyl) isocyanuric acid ester, three [(3, 5-di-tert-butyl-hydroxy phenyl) propionyl oxygen base ethyl] isocyanuric acid ester, 3, 9-two [1, 1-dimethyl-2-{ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl oxygen base } ethyl]-2, 4, 8, 10-tetra-oxaspiros [5, 5] undecane.
As the phenol antioxidant using in the present invention, also can use commercially available product, for example, can enumerate: イ Le ガ ノ Star Network ス 1010 (Ciba company systems), イ Le ガ ノ Star Network ス 1076 (Ciba company systems), イ Le ガ ノ Star Network ス 1330 (Ciba company systems), イ Le ガ ノ Star Network ス 3114 (Ciba company systems), イ Le ガ ノ Star Network ス 1425WL (Ciba company system) etc.
The use level of the above-mentioned phenol antioxidant in the present invention does not limit, and is preferably the scope of 500～5000ppm with respect to above-mentioned whole polypropylene-based resin compositions.More preferably 1000～4000ppm, more preferably 1500～3000ppm.When lower than 500ppm, and reduce by the effect of aftermentioned antioxidant, therefore not preferred.On the contrary, in the situation that exceeding 5000ppm, and saturated by the effect of aftermentioned antioxidant, cause the pollution of the cooling roller in film albefaction and the film making process producing to the movement on film surface due to this antioxidant etc., therefore not preferred.
In the present invention, compared with containing at least one being selected from esters of acrylic acid antioxidant as above, Phosphorus antioxidant and phenol antioxidant, preferably contain the antioxidant of at least two kinds being selected from wherein, more preferably and with the embodiment of three kinds of esters of acrylic acid antioxidant, Phosphorus antioxidant and phenol antioxidant.
Above-mentioned three kinds of antioxidants are not limited to a kind of separately also use.Can be used together two or more in various types of, also can except above-mentioned three kinds of antioxidants, go back and use the antioxidant of other structures such as such as sulphur class antioxidant.
, demonstrate by the effect that the inhibition white point of the unavailable height of combination of known antioxidant is sneaked in the past with above-mentioned multiple antioxidant by also.
Known phenol antioxidant and Phosphorus antioxidant, selectivity for the antioxidant effect of each composition of above-mentioned raw materials resin combination is few, but the affinity of the rubber section of esters of acrylic acid antioxidant and polypropylene-base segmented copolymer is strong, there is the deteriorated tendency of preferential inhibition rubber section.On the other hand, about the generation of white point, large to the deteriorated effect of rubber section.Therefore, infer by and with above-mentioned multiple antioxidant, can make white point significantly reduce.
In addition, surface protection polypropylene resin film of the present invention, the scope that the thickness variation rate of the width of preferred film is 1～10%.Lower than 1% in the situation that, can not produce the problem of quality aspect in thickness variation rate, but thickness needed time lengthening while regulating, therefore economy significantly reduces, so unrealistic.On the other hand, in the situation that thickness variation rate exceedes 10%, the planarity of film (fluctuating and curling) variation, or in the time being wound into roller shape, produce fold and lax, therefore not preferred.Thickness variation rate more preferably 1.5～8%, most preferably is 2～5% scope.
The preparation method who is combined with the polypropylene-based resin composition of the above-mentioned antioxidant using in the present invention, has no particular limits, and can enumerate known method.For example can enumerate: use the mixing rolls such as kneader, Banbury, roller to carry out the mixing method of heating and melting, use single screw rod or twin screw extruder etc. to carry out the mixing method of heating and melting etc.In addition, also various resin particles can be carried out to dry type mixing.In the preparation method of said composition, about this antioxidant, can directly add various powder, also can add with the form of the masterbatch that mixes in above-mentioned polypropylene-based resin in advance.In the situation of adding with the form of masterbatch, can prepare respectively additive, also can mix two or more preparation.In addition, also the commercial resins that is combined with above-mentioned additive can be combined to implement.In addition, for above-mentioned composition, the composition that can previously preparedly supply with in film making process, is re-supplied in the forcing machine that masking uses, also the composition that forms said composition can be supplied in the forcing machine that this masking uses be prepared, masking.
In addition, the amplitude of fluctuation of 20 DEG C of xylene soluble part amounts of above-mentioned film is made as below 2%, film distortion is also very important when preventing coating adhesive.Be preferably below 1%.
As this rate of change is controlled to the method in above-mentioned scope, for example can enumerate: raw material mixed on a small quantity to the method that drops in forcing machine at every turn, the shape of loading hopper is made to the shape of approximate tubular and do not make the method for its segregation, whipping appts is set prevents the method etc. of segregation in loading hopper inside, from production stability, prevent the viewpoints such as dust generation, the method for the anti-locking apparatus partition of segregation is preferably set in loading hopper.Initial produce segregation be due to, in the part of material resin of mixing when the raw material of doping and poor lubrication soft like this from speed large different raw material, for example elastomerics of the inwall landing of the inclination of loading hopper bottom, for along inwall fall raw material with pay the raw material of nearly whereabouts in central authorities, proportioning produce variation.
As segregation prevention method, as follows in aforementioned list like this: 1) producing the method that raw material dropped into before segregation in forcing machine, by a small amount of method of putting in forcing machine of repeatedly mixing of raw material.2) make not produce the method for difference at stock yard, make the method for the shape of approximate tubular by the shape of loading hopper from the speed of loading hopper inwall landing.3) for example, even produce segregation, also do not produce segregation discharge time and install mixing device from loading hopper, insert in vertical direction screw rod and make the method for its rotation for raw material.4) arrange and make the operation that all raw materials fall along wall and the in the situation that of segregation-free, make method that raw material constantly falls in loading hopper, segregation is set in loading hopper prevents the method etc. of partition.In these methods, about 1) and 2), owing to completing, the amount of raw material of mixing is few, and therefore, while having problems in mixing device, raw material is removed at once, therefore, has problem in productivity.About 3) method, due to lasting mixing raw material, therefore there is cutting raw material and easily produce the problem of dust.Thus, industrial 4) method the most useful.
Below, illustrate particularly for completing above-mentioned 4) the shape of device of segregation prevention method, also can in the scope of purport according to the invention, add suitable change to implement, these include in technical scope of the present invention.
This device is characterised in that, by raw materials bucket with in order to make between the inwall of the inclination of this bottom when the partition of the funnel of setting shape is conversely fallen with raw material than how many wide gaps of the size of material resin, non-vibrating in fact mode is fixed on the cover of loading hopper and suspended part forms.The width in this gap is 1.5 times～7 times of maximum length of the material resin that uses, preferably 2 times～5 times.This gap is when more than 7 times, and segregation preventing effectiveness diminishes, and is 1.5 times when following, the danger that exists material resin to pile up.In addition, be below 5 minutes than the bottom of this device time that more the volume preferred feedstock of the loading hopper of below is passed through.If there is 5 minutes above passing through the time, there is the danger that causes segregation after material resin is by this gap.
In addition, the not special regulation of the length of the direction that the raw material in this gap declines, the short person of the narrowest part is difficult to become the obstacle that raw material declines, and is therefore preferably to the maximum below 10cm.In addition, this gap can be arranged on the above-below direction of loading hopper to 2 more than position, but segregation preventing effectiveness when 1 position is abundant, and simple in structure, therefore preferred.In addition, the angle of the bottom of the umbrella part of sprung parts is more than 40 degree with respect to horizontal direction, more preferably more than 50 degree.If lower than 40 degree, the mobile variation of material resin, segregation preventing effectiveness weakens, therefore not preferred.In addition, approach the angle of the tilt internal wall of the raw materials bucket on the top of the bottom of umbrella part, more than being also preferably 40 degree with respect to horizontal direction, more preferably more than 50 degree.If this angle is lower than 40 degree, the also variation that flows of material resin, segregation preventing effectiveness weakens, therefore not preferred.
Be supplied in the forcing machine that this masking uses than the composition of uniform composition forming the mixed with resin that obtains according to aforesaid method, be filmed.
Surface protection of the present invention is characterised in that by the manufacture method of polypropylene resin film,
(1) control of the degree of crystallinity in the cooling conditions control of molten resin
(2) tractive when traction of molten resin, cooling curing is controlled than (draft ratio)
(3) the film width gauge control when traction of molten resin, cooling curing.
(control of the degree of crystallinity in cooling conditions control)
Extruded film of the present invention is the unstretching film obtaining by T die head method masking, and there is no particular limitation for the thickness of film, is generally 1～500 μ m, and preferred thickness is selected as required.
As by polypropylene resin composite of the present invention as the film forming condition of extruded film, preferably at 40～65 DEG C of 200 DEG C～250 DEG C of die head temperatures, chill-roll temperature, carry out.More preferably 45～60 DEG C.Chill-roll temperature during lower than 40 DEG C, can not get for the sufficient degree of crystallinity of heat-resisting dimensional stability, therefore not preferred.On the contrary, exceed in the situation of 65 DEG C, produce the touch roll vestige of cooling roller, therefore not preferred, in addition, also the transparency is extreme sometimes reduces.In addition, about cooling time, be not particularly limited, but be preferably 0.5 second above scope.Cooling time, cooling performance was insufficient during lower than 0.5 second, therefore, produced the touch roll vestige of cooling roller, therefore not preferred.On the other hand, the upper limit of cooling time, from the viewpoint of the degree of crystallinity of film, there is no particular limitation, from the viewpoint of economy, productivity, more preferably below 5 seconds, preferably more than 2 seconds.In addition, must be lower time, can be also more than 3 seconds by Temperature Setting.
As the method for any adjusting degree of crystallinity, in the situation that also using nucleating agent, worry that the white point of film described above increases, therefore need to add below 100ppm.Therefore find, carry out crystallization control degree according to the cooling conditions control of the molten resin of cooling conditions.
(control of tractive ratio)
Extruded film of the present invention, by by the tractive in the traction operation after melt extruding than being adjusted in 0.4～3.0 scope, the degree of birefringence of film can reach the scope of regulation.The film forming condition of common known tractive beguine under according to this calculates.
Tractive ratio=(film pulling speed/die head exit molten resin speed) ÷ air gap
Air gap refers to from die head exit till draw the distance (cm) that (cooling) roller, molten resin joins.
At tractive, than lower than 0.4 in the situation that, the thickness spot of film increases, and reduces in the bonding planarity that adds film in man-hour, therefore not preferred.In addition, at tractive than exceed 3.0 in the situation that, the problem that scope, the shock-resistance that exists degree of birefringence to exceed regulation significantly reduces, the mechanical characteristic of film self reduces, therefore not preferred.
[film width gauge control]
As the control method of film width thickness, can enumerate: the method that regulates manually or automatically die lip gap.As the method for dwindling thickness variation in shorter time, preferably automatically regulate the method for compressed gap by machinery or hot bolt mode.In addition, in addition, need to regulate the condition of wind box, be below 10% by the thickness variation control of width.Wind box is that the resin molding air blowing to adhering on cooling roller makes its device closely sealed on cooling roller, if while air blowing from the air increase of the clearance leakage of wind box top and cooling roller, due to the air leaking, the resin molding before contacting with cooling roller produces fluctuating, the thickness change of film width.Therefore, need to make the blast in wind box certain on width, more than needing the absolute value of blast not to be increased to necessity simultaneously.The blast of wind box is determined according to the pulling speed of film, is preferably below 20mmHg.
Also can utilize the method for common industrial employing to implement the surface treatment such as Corona discharge Treatment or the scorching processing of fire to extruded film of the present invention.
In the present invention, very important for the surface protection film that binder layer forms being set in above-mentioned surface protection with at least one side of polypropylene resin film.According to this correspondence, can effectively apply flexibly the feature of the polypropylene resin film of the invention described above, the applicability as protective membrane in wide spectrum improves.Particularly as preventing for example at electronics such as the associated materials such as liquid crystal panel or polaroid, precise product, adhering to of scuffing when the processing of parts and associated components or assembling or dust, the method of the splicing ear portion of the purposes of pollution etc. or partly plating flexible print wiring board etc., hide at non-plating portion laminating bonding film, carry out afterwards the method for plating, use in the plating such as resist film or the method for etching block film and etch processes that in etching work procedure while manufacture with shadow mask board, protection arranges on non-etched face, by stacked film on the face that there is no circuit of semiconductor element, the surface of protection semiconductor element, thereby the method for the simplification of the technique while realizing assembled semiconductor device etc. particularly as require to suppress to pollute and strong various precise products or the protection of parts and processing and the assembling procedure of this goods or parts of shortcoming in protective membrane preferably use.In addition, the heat-resisting excellent size stability of polypropylene resin film of the present invention, in above-mentioned bonding processing, even if for example improve the drying temperature of drying process, also suppresses the generation that hot fold and film are lax, therefore, can improve the productivity of this bonding processing.In addition, can suppress the generation by hot fold and the lax defective products causing of film.
Kind, thickness and the bounding forces etc. of above-mentioned binder layer do not limit.Can suitably select according to market demands.In addition, the laminating method of this binder layer does not also limit.Can by coating method and extrude layered manner any one carry out.
Embodiment
Below, enumerating embodiment carries out more specifically bright to the present invention, but the present invention is not subject to the restriction of following embodiment, also can in the scope that can be applicable to purport of the present invention, add suitable change to implement, these include in technical scope of the present invention.
1. melt flow rate (MFR) [MFR]
According to JIS K7210, method by condition-14 (loading 2.16kg, temperature 230 DEG C at) is measured.
2. ethylene content
The method of recording in 616 pages by polymer handbook (nineteen ninety-five, Kinokuniya bookstore distribution) is measured with 13C-NMR method.
The ratio (%) of the xylene soluble part in 3.20 DEG C
Sample 5g after complete melting, is cooled to 20 DEG C in boiling xylene 500ml, places more than 4 hours.Afterwards, filtering separation becomes precipitate and solution, by dry filtrate, under reduced pressure, be dried at 70 DEG C.By 20 DEG C of xylene soluble part amounts of quality determination of obtained dry thing, obtain this ratio.
4. the degree of crystallinity of film
Use wide-angle x-ray diffraction transmission method (RIGAKU RINT2500) to measure.
5. kinetic friction coefficient
To between the sealing aspect of laminating film, be combined, measure oilness based on JIS-K7215-1987.
6. thickness variation rate
According to JIS K7130, use the リ ニ ア ゲ mono-ジ タ イ プ SIS-6 of the rugged making manufacturing of tail, measure 1 of the wide membrane sample of 1m with width 3cm spacing, calculate mean thickness.Then, use in maximum value in the membrane sample of measuring or minimum value and large any one of the difference of mean thickness, with following calculating formula calculating.
Thickness variation rate (%)=| (mean thickness)-(maximum value or minimum value) |/(mean thickness) × 100
7. Young's modulus
According to JIS K7127, using sample shape is the test film (sample length 200mm, the wide 15mm of sample, spacing jig are from 100mm) of No. 1 shape, under the pinblock speed condition of 500mm/ minute, measures at 23 DEG C for MD direction (film length direction).
8. (△ n) for degree of birefringence
Use Abbérefractometer, measure the specific refractory power Nx of film travel direction and the specific refractory power Ny with membrane flow direction orthogonal direction, use following formula to calculate.
△n=|Nx-Ny|
The variation wide (%) of the xylene soluble part in 8.20 DEG C
By 1 of membrane sample wide 1m with width and longitudinally 3cm spacing sample, measure 20 DEG C of xylene soluble part amounts by the method for above-mentioned record, the maximum value of obtaining the data of 10 points deducts minimum value and the value that obtains.
9. thermal distortion patience
The film of moulding is cut into: 5cm on travel direction × with respect to the transversely 25cm of flow direction, flatly diaphragm is carried out to 5 minutes heat treated in the xeothermic baking oven at 120 DEG C under the state that keeps both ends with metal frame.After heat treated, take out at once from baking oven, at room temperature naturally cooling is after 30 minutes, and in following scope, visual observation is by sagging (elongation) state of the own wt generation of film.
Zero: without sagging or almost do not have.
△: observe slight sag state.
×: observe hang.
10. fold, lax evaluate (1)
For the film of moulding, visual observation and fold during with the roller of cutting machine (K.K. Totada processed SXR-140 type) curling film long 100m wide with 1300mm, lax generation situation.
Zero: in movement and while batching, do not produce fold, lax.
△: slightly observe fold, lax generation in movement or while batching.
×: in movement or while batching, obviously observe fold, lax generation.
Lax evaluate (2) of 11. folds
Visual observation is preserved the fold after 30 days, lax generation Zhuan Condition by above-mentioned fold, the lax film roller that batches in (1) evaluated at 23 DEG C of humidity 50RH%, temperature.
Zero: do not produce fold, lax.
△: observe fold, lax generation.
×: obviously observe fold, lax generation.
Distortion after 18. adhesive coated
Use the silk rod Japanese synthetic chemistry system of coating " コ mono-Port ニ mono-Le 8694 ", make the thickness of tackiness agent reach 3～5 μ m, then, be dried 5 seconds at 70 DEG C.Film after smooth place expansion adhesive coated, Visual Confirmation has or not distortion.
Zero: without distortion
△: slightly have distortion
×: there is distortion
12. film albefactions
By 180 ° of bending tablets, fold after rib the visual albefaction being determined with without the kink in when expansion.
◎: do not produce albefaction.
Zero: slightly observe albefaction.
△: observe albefaction.
×: obviously observe albefaction.
13. mist degrees
According to JIS-K-6714, use Japan's essence mechanism to make made " mist degree tester J " and measure.
14. resistance to adhesives
According to ATM-D1893-67, on the area of A4 size, apply the loading of 90N, under 60 DEG C of atmosphere, place after 2 hours, remove loading, under the condition of translational speed 100mm/ minute, measure by the peel resistance of the aluminium bar of φ 5.
15. shock strengths
According to ASTM D3420, it is longitudinally 55～60cm that sample cuts into, and is laterally 9～10cm.At the indoor use shock-testing machine of 23 DEG C, the intensity level while reading punching is to below radix point the 1st.Repeatedly carry out this operation 10 times, try to achieve its mean value.
16. white points
The film of moulding is cut into: 33.3cm on flow direction × with respect to the transversely 30cm of flow direction, be placed on the plate that irradiates luminescent lamp from film, observes white point more than instrumentation 0.1mm by transmitted light is visual.Then, white point after counting is impregnated in liquid nitrogen, under the state of hardening, cut into half point with razor, by the section with 50～300 times of these white points of observation with microscope, if do not become the material of core, for example impurity taking Mierocrystalline cellulose etc. as representative not, the white point that is judged to be the piece of not melting, produces for the piece of the part generation gelation of raw material, by the gel of the deteriorated piece causing of part of the material being shaped etc.In the situation that thering is core, be judged to be the white point that impurity causes, when counting, foreclose.
(embodiment 1)
By sym-propene polymer resin (MFR=7) 69 weight parts, rubber constituent amount is 13.0%, ethylene content is 6.5% block copolymerization polypropylene resin (MFR=2) 22 weight parts, elastomerics (trade(brand)name: タ Off マ mono-P0480) 7 weight parts that Mitsui Chemicals, Inc manufactures and master batch resin 2 weight parts melt extrude with the T die head film-making machine of the automatic thickness control function with hot bolt type, described master batch resin comprises: the esters of acrylic acid antioxidant being made up of the sym-propene polymer resin (MFR=7) that contains ス ミ ラ イ ザ mono-GS (Sumitomo Chemical Co's system) 5 % by weight as esters of acrylic acid antioxidant, 2.0 seconds cooling times (film speed 60m/ minute) at 60 DEG C of chill-roll temperature, the tractive when traction of molten resin is than 1.56 (die lip gaps: 0.5mm, die lip outlet molten resin speed: 4.8m/ minute, air gap: 8cm), under the film forming condition of wind box blast 10mmHg, obtain the unstretching film of thickness 40 μ m.In addition, it is 230,240 and 235 DEG C by the resin temperature settings separately of the drainage area of above-mentioned forcing machine, mixing district and metering zone.The results are shown in table 1.
The polypropylene resin film obtaining in the present embodiment, any one characteristic shown in table 1 is all good, is high-quality.
(embodiment 2)
Coordinate and contain as イ Le ガ ホ ス 168 (Ciba Co., Ltd. system) the 0.15 quality % of Phosphorus antioxidant and block copolymerization polypropylene resin (MFR=2) 95 weight parts that are 6.5% as rubber constituent amount 13.0%/ethylene content of イ Le ガ ノ Star Network ス 1010 (Ciba Co., Ltd. system) the 0.18 quality % of phenol antioxidant, atactic copolymerized polypropene resin (MFR=7) 5 weight parts of ethylene content 3.0%, setting chill-roll temperature is 45 DEG C, in addition, obtain the polypropylene resin film of embodiment 2 by method similarly to Example 1.The results are shown in table 1.
The polypropylene resin film obtaining in the present embodiment, any one characteristic shown in table 1 is all good, is high-quality.
(embodiment 3)
Coordinate and contain as イ Le ガ ホ ス 168 (Ciba Co., Ltd. system) the 0.15 quality % of Phosphorus antioxidant and as sym-propene polymer resin (MFR=7) 85.5 weight parts of イ Le ガ ノ Star Network ス 1010 (Ciba Co., Ltd. system) the 0.15 quality % of phenol antioxidant, elastomerics (trade(brand)name: タ Off マ mono-P0480) 14.5 weight parts that Mitsui Chemicals, Inc manufactures, setting chill-roll temperature is 50 DEG C, tractive ratio when the traction of molten resin is 2.50 (die lip gaps: 0.8mm, die lip outlet molten resin speed: 3.0m/ minute, air gap: 8cm), in addition, obtain the polypropylene resin film of embodiment 3 by method similarly to Example 1.The results are shown in table 1.
The polypropylene resin film obtaining in the present embodiment, has equal characteristic with the polypropylene resin film obtaining in embodiment 1, is high-quality.
(embodiment 4)
By sym-propene polymer resin (MFR=7) 73 weight parts, rubber constituent amount is that 13.0%/ethylene content is 6.5% block copolymerization polypropylene resin (MFR=2) 23 weight parts, elastomerics (trade(brand)name: タ Off マ mono-P0480) 12 weight parts that Mitsui Chemicals, Inc manufactures and master batch resin 2 weight parts are put into and in forcing machine, are carried out melting by having the raw materials bucket of the anti-locking apparatus of segregation, melt extrude with the T die head film-making machine of the automatic thickness control function with hot bolt type, described master batch resin comprises: the esters of acrylic acid antioxidant being made up of the sym-propene polymer resin (MFR=7) that contains ス ミ ラ イ ザ mono-GS (Sumitomo Chemical Co's system) 5 % by weight as esters of acrylic acid antioxidant, 2.0 seconds cooling times (film speed 60m/ minute) at 60 DEG C of chill-roll temperature, the tractive when traction of molten resin is than 1.56 (die lip gaps: 0.5mm, die lip outlet molten resin speed: 4.8m/ minute, air gap: 8cm), under the film forming condition of wind box blast 10mmHg, obtain the unstretching film of thickness 40 μ m.In addition, it is 230,240 and 235 DEG C by the resin temperature settings separately of the drainage area of above-mentioned forcing machine, mixing district and metering zone.In addition, carry out the gauge control of width.The results are shown in table 1.
The polypropylene resin film obtaining in the present embodiment, any one characteristic shown in table 1 is all good, is high-quality.
(embodiment 5)
Coordinate and contain as イ Le ガ ホ ス 168 (Ciba Co., Ltd. system) the 0.15 quality % of Phosphorus antioxidant and as sym-propene polymer resin (MFR=7) 90 weight parts of イ Le ガ ノ Star Network ス 1010 (Ciba Co., Ltd. system) the 0.15 quality % of phenol antioxidant, elastomerics (trade(brand)name: タ Off マ mono-P0480) 10 weight parts that Mitsui Chemicals, Inc manufactures, setting chill-roll temperature is 50 DEG C, tractive ratio when the traction of molten resin is 2.50 (die lip gaps: 0.8mm, die lip outlet molten resin speed: 3.0m/ minute, air gap: 8cm), in addition, obtain the polypropylene resin film of embodiment 2 by method similarly to Example 4.The results are shown in table 1.
The polypropylene resin film obtaining in the present embodiment, have with embodiment 4 in the equal characteristic of the polypropylene resin film that obtains, be high-quality.
(embodiment 6)
Put in forcing machine by the raw materials bucket that does not possess the anti-locking apparatus of segregation, material resin is carried out to melting, in addition, obtain the polypropylene resin film of embodiment 6 by method similarly to Example 4.The results are shown in table 2.
(comparative example 1)
To coordinate ethylene content be atactic copolymerized polypropene resin (MFR=7) 30 weight parts of 0.5 quality % and contain as イ Le ガ ホ ス 168 (Ciba Co., Ltd. system) the 0.22 quality % of Phosphorus antioxidant and be that 8.5%/ethylene content is 5.0% block copolymerization polypropylene resin (MFR=2) 70 weight parts as the rubber constituent amount of イ Le ガ ノ Star Network ス 1010 (Ciba Co., Ltd. system) the 0.28 quality % of phenol antioxidant, in addition, obtain the polypropylene resin film of comparative example 2 by method similarly to Example 1.The results are shown in table 2.
The polypropylene resin film obtaining in this comparative example produces fold, lax in film roller is preserved.
(comparative example 2)
Coordinating ethylene content is atactic copolymerized polypropene resin (MFR=7) 98 weight parts of 0.5 quality %, master batch resin (M-1) 1 weight part, with master batch resin 1 weight part, wherein, described master batch resin (M-1) comprises: by containing as two (2 of organic phosphoric acid ester cpds, 2 '-methylene radical-bis-(4, 6-di-tert-butyl-phenyl) phosphoric acid ester)-aluminium hydroxide salt (Asahi Denka Kogyo K. K's system, ア デ カ ス タ Block NA-21) 1 % by weight sym-propene polymer resin (MFR=7) form nucleating agent, described master batch resin comprises: by containing the esters of acrylic acid antioxidant forming as the sym-propene polymer resin (MFR=7) of ス ミ ラ イ ザ mono-GS (Sumitomo Chemical Co's system) 5 % by weight of esters of acrylic acid antioxidant, melt extrude with T die head film-making machine, 3.0 seconds cooling times (film speed 40m/ minute) at 45 DEG C of chill-roll temperature, the tractive when traction of molten resin is than 1.60 (die lip gaps: 0.5mm, die lip outlet molten resin speed: 8.0m/ minute, air gap: 8cm) film forming condition under obtain the unstretching film of thickness 100 μ m.The results are shown in table 2.The polypropylene resin film obtaining in this comparative example also produces fold, lax in film roller is preserved.
(comparative example 3)
Coordinate and contain as イ Le ガ ホ ス 168 (Ciba Co., Ltd. system) the 0.15 quality % of Phosphorus antioxidant and as block copolymerization polypropylene resin (MFR=2) 100 weight parts of rubber constituent amount 11.0%/ethylene content 20% of イ Le ガ ノ Star Network ス 1010 (Ciba Co., Ltd. system) the 0.18 quality % of phenol antioxidant, in addition, obtain the polypropylene resin film of comparative example 3 by method similarly to Example 1.The results are shown in table 2.
The thermal distortion patience of the polypropylene resin film obtaining in this comparative example is insufficient.
(comparative example 4)
Except wind box blast is set as 40mHg, obtain the polypropylene resin film of comparative example 4 by method similarly to Example 1.The results are shown in table 2.
The polypropylene resin film obtaining in this comparative example produces fold, lax in film roller is preserved.
(comparative example 5)
Coordinating ethylene content is atactic copolymerized polypropene resin (MFR=7) 97 weight parts of 0.5 quality %, and master batch resin 1 weight part, elastomerics (trade(brand)name: タ Off マ mono-P0480) 2 weight parts that Mitsui Chemicals, Inc manufactures, wherein, described master batch resin comprises: by containing the esters of acrylic acid antioxidant forming as the sym-propene polymer resin (MFR=7) of ス ミ ラ イ ザ mono-GS (Sumitomo Chemical Co's system) 5 % by weight of esters of acrylic acid antioxidant, in addition, obtain the polypropylene resin film of comparative example 5 by method similarly to Example 4.The results are shown in table 2.
The polypropylene resin film obtaining in this comparative example, easily there is albefaction in film, and not only thermal distortion patience variation also produces fold, lax in film roller is preserved.
(comparative example 6)
Coordinate and contain as イ Le ガ ホ ス 168 (Ciba Co., Ltd. system) the 0.22 quality % of Phosphorus antioxidant and as block copolymerization polypropylene resin (MFR=7) 22 weight parts of rubber constituent amount 13%/ethylene content 6.5% of イ Le ガ ノ Star Network ス 1010 (Ciba Co., Ltd. system) the 0.28 quality % of phenol antioxidant, sym-propene polymer resin (MFR=7) 57 weight parts, elastomerics (trade(brand)name: タ Off マ mono-P0480) 2 weight parts and master batch resin 1 weight part that Mitsui Chemicals, Inc manufactures, described master batch resin comprises: by containing the esters of acrylic acid antioxidant forming as the sym-propene polymer resin (MFR=7) of ス ミ ラ イ ザ mono-GS (Sumitomo Chemical Co's system) 5 % by weight of esters of acrylic acid antioxidant, put into and in forcing machine, carry out melting by possessing the raw materials bucket of the anti-locking apparatus of segregation similarly to Example 1, melt extrude with the T die head film-making machine of the automatic thickness control function with hot bolt type, 3.0 seconds cooling times (film speed 40m/ minute) at 45 DEG C of chill-roll temperature, the tractive when traction of molten resin is than 0.63 (die lip gap: 0.5mm, die lip outlet molten resin speed: 8.0m/ minute, air gap: 8cm) film forming condition under obtain the unstretching film of thickness 100 μ m.The results are shown in table 2.The polypropylene resin film obtaining in this comparative example, there is distortion in the film after adhesive coated.
(comparative example 7)
Except not carrying out, the gauge control of width, obtaining the polypropylene resin film of comparative example 7 by method similarly to Example 4.The results are shown in table 2.
The polypropylene resin film obtaining in this comparative example, produces fold, lax in the movement of film and in the preservation of film roller.
(reference example 1)
In the method for comparative example 1, except adding master batch resin (M-1) 5 weight parts that contain nucleating agent, obtain the polypropylene resin film of reference example 3 by the method same with comparative example 1.The results are shown in table 3.
The white point of the polypropylene resin film obtaining in this reference example significantly increases compared with the polypropylene resin film obtaining in comparative example 1, for low-quality.
The above results is shown in to table 1, table 2.
Table 1
Table 2
Figure GDA0000399715060000251
The possibility of utilizing in industry
Heat-resisting dimensional stability of the present invention and planarity are good, and shock-resistance and laminating excellent processability are for example preferred as the base material film of protective membrane.
The heat-resisting excellent size stability of polypropylene resin film for surface protection of the present invention; therefore; the secondary processing such as such as bonding processing adapt to good; also suppress hot fold and the lax generation of film even if the processing such as be particularly dried under near the high temperature 130 DEG C; thereby, can improve this secondary processing productivity, suppress the generation by the lax defective products causing of hot fold and film.
In addition, thickness spot of the present invention is little.
In addition, polypropylene resin film of the present invention does not preferably contain in fact anti blocking agent, for example can avoid in the case of the film that makes to contain anti blocking agent moves, because wearing and tearing wait the problem coming off that causes anti blocking agent, therefore pollution and obstacle generation etc. that, inhibition is caused by this cast.
In addition, although the present invention does not contain in fact lubricant and anti blocking agent, surfaceness is suitable, and the oilness of film and resistance to adhesive are good, and rigidity is good, thereby the treatability of film is good.
In addition, because the transparency is good, therefore the visibility of packed article and protected body is good.
In addition, owing to having film strength, therefore, treatability is good.
In addition, although above-mentioned heat-resisting dimensional stability improves, shock strength is also good, keeps by be made up of the formedness of the shock-resistance of giving block polypropylene resinoid, and the reliability while use as protective membrane is high.

Claims (7)

1. a surface protection polypropylene resin film, is characterized in that,
In fact taking polypropylene-based resin as principal constituent, 20 DEG C of xylene soluble part amounts exceed 9% and lower than 16%, the containing ratio of nucleating agent is below 100ppm, and the thickness variation rate of the width of film is more than 1% and below 10%, the degree of crystallinity of film is 34～65%, and degree of birefringence △ n is 0.4 × 10 -3～2.5 × 10 -3, the content of the anti blocking agent in film is below 50ppm, and kinetic friction coefficient is below 1.0, and modulus in tension is that 500MPa is above and below 900MPa, the moving rate of 20 DEG C of xylene soluble partial quantitative changes of described film is below 2%.
2. surface protection polypropylene resin film according to claim 1, is characterized in that,
The resistance to adhesive of described film is below 10mN.
3. surface protection polypropylene resin film according to claim 1, is characterized in that,
Maximum diameter in described film is that white point more than 0.2mm is 0/m 2, and the white point that maximum diameter is less than 0.2mm is 100/m 2below.
4. surface protection polypropylene resin film according to claim 1, is characterized in that,
Longitudinal Young's modulus at 23 DEG C of described film is more than 500Mpa.
5. surface protection polypropylene resin film according to claim 1, is characterized in that,
Shock strength at 23 DEG C of described film is more than 0.3J.
6. surface protection polypropylene resin film according to claim 1, is characterized in that,
Described film at least contains esters of acrylic acid antioxidant, and contains at least one antioxidant being selected from Phosphorus antioxidant and phenol antioxidant.
7. a surface protection film, is characterized in that, at least one side of the surface protection in claim 1～6 described in any one with polypropylene resin film, binder layer is set and obtains.
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