CN102791480B - Mold release film and method for manufacturing mold release film - Google Patents

Mold release film and method for manufacturing mold release film Download PDF

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Publication number
CN102791480B
CN102791480B CN201180013457.0A CN201180013457A CN102791480B CN 102791480 B CN102791480 B CN 102791480B CN 201180013457 A CN201180013457 A CN 201180013457A CN 102791480 B CN102791480 B CN 102791480B
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mold release
release film
mentioned
top layer
friction treatment
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CN102791480A (en
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中尾洋祐
松本弘丈
五藤靖志
土谷雅弘
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Abstract

Disclosed is a mold release film, which has excellent mold releasability and excellent conforming characteristics to the substrate surface, and which can suppress flow out of an adhesive in heat press molding. The mold release film has a surface layer, and a mold release layer is observed only in a region within a thickness of 50-300 nm from the surface of the surface layer.

Description

The manufacture method of mold release film and mold release film
Technical field
The present invention relates to that a kind of release property is excellent and tracing ability for substrate surface is excellent, the mold release film of the outflow of bonding agent when can suppress hot forming.
Background technology
In the manufacturing process of printed circuit board, flexible printed circuit board, multilayer printed-wiring board etc., on substrate when hot pressing copper-clad laminated board or Copper Foil, using mold release film across prepreg or heat-resistant film.In addition, in the manufacturing process of flexible printed circuit board, on the flexible printed circuit board body being formed with copper circuit, when utilizing heat curable adhesive or thermohardening type adhesive sheet to be hot bonding by cover layer, in order to prevent cover layer and heating platen from occurring bonding, also widely use mold release film.
Require following performance to mold release film, such as, ability is by the heat resistance of hot forming, relative to performances such as the release property of printed circuit board and heating platen, the easiness of waste treatment.In addition, in order to goods yields during hot forming improves, the performance polluted is not produced to copper circuit also very important.
In the past, as mold release film, use the PETG film, polymethylpentene film, polypropylene screen etc. (such as, patent document 1) of fluorine mesentery, coating silicone always.
But the heat resistance of fluorine mesentery, release property, non-polluting are excellent, but not only high price, and during burning in waste treatment, be difficult to burning, also can produce toxic gas.In addition, the coating PETG film of silicone and polymethylpentene film, the transfer due to the low-molecular weight in silicone or constituent can cause the pollution of printed circuit board especially copper circuit, likely damages quality.In addition, the poor heat resistance of polypropylene screen, release property is also insufficient.
In addition, be investigated the mold release film formed by polyester based resins such as polybutylene terephthalate (PBT)s, the heat resistance of mold release film although it is so, the easiness of waste treatment, non-polluting are excellent, but also need to improve in release property.
To this, and mold release film that release property also excellent excellent as non-polluting, applicant has invented the mold release film be made up of the polypropylene of polyester based resin and ormal weight, is disclosed in patent document 2.At this, in order to make, the release property of the mold release film described in patent document 2 is further tremendous to be improved, and also as described in patent document 2, it is effective for implementing heat treated way to mold release film.
But such heat treatment is at high temperature carried out and is needed the long period, therefore causes the increase of cost sometimes.And, implementing heat treated mold release film due to the flexibility of film entirety reduces, therefore the concavo-convex tracing ability (imbedibility) for substrate surface reduces, such as, space can be produced during hot forming, or sometimes produce the electrode section that the bonding agent being formed at cover layer flows out to flexible printed circuit board, become the unfavorable conditions such as the obstacle of the plating process of electrode section.Thus, a kind of mold release film do not damaged concavo-convex tracing ability to substrate surface, there is more excellent release property is needed.
Patent document
Patent document 1: Japanese Unexamined Patent Publication 5-283862 publication
Patent document 2: Japanese Unexamined Patent Publication 2009-132806 publication
Summary of the invention
The problem that invention will solve
The object of the invention is to provide a kind of release property excellent and tracing ability for substrate surface is excellent, the mold release film of the outflow of bonding agent when can suppress hot forming.
Solve the method for problem
1st aspect of the present invention is the mold release film with top layer, wherein, only can observe demoulding processing layer in the region of the surface from above-mentioned top layer to thickness 50 ~ 300nm.
2nd aspect of the present invention is the mold release film on the top layer had containing polyester based resin, wherein, from region to thickness 1 μm, the surface on above-mentioned top layer, in carbonyl contained in above-mentioned polyester based resin is more than 45% relative to the ratio of the face carbonyl of orientation abreast.
3rd aspect of the present invention is the mold release film with top layer, and wherein, the surface roughness Rz on above-mentioned top layer is 250 ~ 450nm, and the degree of skewness Rsk on surface is+0.3 ~+1.1, and the steepness Rku on surface is 5 ~ 11.
Below, the present invention is described in detail in detail.
The discoveries such as the present inventor: for having these 3 kinds of top layers following, namely, (1) top layer of the demoulding processing layer of regulation can be observed, (2) meet the top layer of the scope of regulation and (3) surface roughness Rz, the degree of skewness Rsk on surface and the steepness Rku on surface relative to the ratio of the face carbonyl of orientation abreast and meet for the mold release film on any one top layer in the top layer of the scope of regulation, the tracing ability for substrate surface can not be damaged, the outflow of bonding agent during suppression hot forming, show excellent release property simultaneously, thus complete the present invention.
The mold release film of the 1st aspect of the present invention has top layer, and only can observe demoulding processing layer in the region of the surface from above-mentioned top layer to thickness 50 ~ 300nm.
In this description, so-called demoulding processing layer, refers to that have the outward appearance different from other regions in top layer, that release property is excellent layer.In addition, in this description, not only comprise the situation that demoulding processing layer middle level entirety has the same outward appearance, although also comprise the position partly comprising and there are other outward appearances, the overall situation forming 1 layer.
For above-mentioned demoulding processing layer, compared with other regions in above-mentioned top layer, different forms can be observed.As the form can observed in above-mentioned demoulding processing layer, such as, the form etc. of the striated parallel relative to face can be enumerated.The form can observed in other regions in above-mentioned top layer is not particularly limited, such as, can enumerate sand shape, the form such as vortex-like, and uneven form etc. other than the above.
Fig. 1,2 and 3 is profiles of the part on the top layer of the mold release film schematically showing the 1st aspect of the present invention.In Fig. 1,2 and 3, upside is the surface on top layer, that is, the surface of mold release film.The part on Fig. 1, the top layer shown in 2 and 3, has the demoulding processing layer 1 of the form observing the striated parallel relative to face in face side.In Fig. 1, other regions 2 in top layer have the form of sand shape, and in Fig. 2, other regions 2 ' in top layer have vortex-like form, in Fig. 3, and other regions 2 in top layer " there is other uneven forms.
The demoulding processing layer observed like this is high density, and plays a role as barrier layer, and therefore above-mentioned top layer is with when such as epoxy bonding agent connects, and can suppress soaking into of epoxy bonding agent.Therefore, the mold release film of the 1st aspect of the present invention can embody excellent release property.
The method of observing above-mentioned demoulding processing layer is not particularly limited, but observes the method for the section using slicer to obtain in thickness direction cut-out preferably by transmission electron microscope.In addition, as the method for observing above-mentioned demoulding processing layer, the method utilizing polarizing microscope, AFM etc. to observe the section that use slicer etc. obtains in thickness direction cut-out can be adopted.Above-mentioned transmission electron microscope (TEM) is not particularly limited, such as, can enumerate Hitachi's transmission electron microscope (model H-9500, Hitachi's high-tech company system) etc.In addition, above-mentioned slicer is not particularly limited, such as, can enumerate sliding microtome (model SM2000-R, Ikeda physics and chemistry Inc.) etc.
In addition, the mold release film of the 1st aspect of the present invention only has demoulding processing layer in the region of the surface from above-mentioned top layer to thickness 50 ~ 300nm, therefore, due to the improvement of release property, thus the mold release film in the past such as implementing heat treatment etc. is different from, both there is excellent release property, film flexibility on the whole can have been maintained again.Therefore, the mold release film of the 1st aspect of the present invention is excellent for the tracing ability of substrate surface, and the outflow of bonding agent when can suppress hot forming.
The thickness of above-mentioned demoulding processing layer is from the surface on above-mentioned top layer to when being less than 50nm, above-mentioned top layer, and such as cannot suppress soaking into of when connecting with epoxy bonding agent epoxy bonding agent fully, the release property of the mold release film obtained can reduce.The thickness of above-mentioned demoulding processing layer is that the flexibility of the mold release film of gained reduces, and the tracing ability for substrate surface reduces from the surface on above-mentioned top layer to during more than 300nm, the outflow of bonding agent when being difficult to suppression hot forming.
The thickness of above-mentioned demoulding processing layer is preferably from the surface on above-mentioned top layer to more than 70nm, and preferably from the surface on above-mentioned top layer to below 250nm.
The mold release film of the 2nd aspect of the present invention has the top layer containing polyester based resin.
For the mold release film of the 2nd aspect of the present invention, in the region of the surface from above-mentioned top layer to thickness 1 μm, in carbonyl contained in above-mentioned polyester based resin is more than 45% relative to the ratio of the face carbonyl of orientation abreast.
In this description, the ratio X relative to the face carbonyl of orientation abreast in carbonyl contained in polyester based resin, is calculated by following formula (1).
X＝{A/(A+B)}×100 (1)
In formula (1), A represents and resolves by X-ray the peak intensity relative to the face carbonyl of orientation abreast obtained, and B represents and resolves by X-ray the peak intensity relative to the face vertically carbonyl of orientation obtained.In this description, parallel or vertically refer to for the surface of mold release film, towards parallel direction or vertical direction relative to face.
Be in above-mentioned scope by the above-mentioned ratio relative to the face carbonyl of orientation abreast, thus the mold release film of the 2nd aspect of the present invention can embody excellent release property.Can infer this be due to: from region to thickness 1 μm, the surface on above-mentioned top layer, by increasing relative to the ratio of the face carbonyl of orientation abreast, thus the hydrophobicity on the surface on above-mentioned top layer can increase.
In addition, in the mold release film of the 2nd aspect of the present invention, the above-mentioned ratio relative to the face carbonyl of orientation is abreast the region in above-mentioned scope, the region of surface to thickness 1 μm from above-mentioned top layer, therefore, due to the improvement of release property, be thus different from the mold release film in the past such as implementing heat treatment etc., both there is excellent release property, film flexibility on the whole can have been maintained again.Therefore, the mold release film of the 2nd aspect of the present invention is excellent for the tracing ability of substrate surface, the outflow of bonding agent when can suppress hot forming.
When the above-mentioned ratio relative to the face carbonyl of orientation is abreast less than 45%, the hydrophobicity on the surface on above-mentioned top layer reduces, and the release property of the mold release film therefore obtained can reduce.
Preferably the above-mentioned ratio relative to the face carbonyl of orientation is abreast more than 55%.
The above-mentioned upper limit relative to the face ratio of the carbonyl of orientation is abreast not particularly limited, and also can be 100%, but is preferably less than 90%.When the above-mentioned ratio relative to the face carbonyl of orientation is abreast more than 90%, such as, the work done energy of friction treatment when manufacturing mold release film becomes excessive, therefore sometimes in the mold release film obtained, produces fold, scar equivalent damage.
The above-mentioned ratio relative to the face carbonyl of orientation is abreast more preferably less than 70%.
As the method for carrying out above-mentioned X-ray parsing, such as, the method (In-PLane) etc. of diffraction that make X-ray oblique incidence relative to the surface on above-mentioned top layer, that measure X-ray can be enumerated.In addition, be not particularly limited for the X-ray resolver carrying out above-mentioned X-ray parsing, such as, film evaluation sample horizontal type X-ray diffraction device (model Smart Lab, society of science system) etc. can be enumerated.
The mold release film of the 3rd aspect of the present invention has top layer, and the lower limit of the surface roughness Rz on above-mentioned top layer is 250nm.When above-mentioned surface roughness Rz is less than 250nm, the top layer obtained becomes level and smooth and the contact area on top layer increases, and release property reduces.The preferred lower limit of above-mentioned surface roughness Rz is 280nm.
In addition, the upper limit of above-mentioned surface roughness Rz is 450nm.When above-mentioned surface roughness Rz is more than 450nm, the concavo-convex increase on the top layer obtained, such as, during for the mobility such as epoxy adhesive or flexibility high clung body, can increase with the contact area of clung body, become the reason that release property reduces.
In this description, so-called surface roughness Rz refers to following value: for the surface on top layer, by starting to be set to Yp1, Yp2, Yp3, Yp4 and Yp5 respectively to the absolute altitude of the 5th projection highly from the highest projection in datum length L, by when being set to Yv1, Yv2, Yv3, Yv4 and Yv5 respectively from the darkest absolute altitude being recessed to the depression of the 5th degree of depth, by the value that following formula (2) is tried to achieve, value means more greatly on surface integral more coarse, and the less surface of value means on surface integral more level and smooth.
Rz＝(|Yp1+Yp2+Yp3+Yp4+Yp5|+|Yv1+Yv2+Yv3+Yv4+Yv5|)/5 (2)
The lower limit of the degree of skewness Rsk on the surface on above-mentioned top layer is+0.3.When the degree of skewness Rsk on above-mentioned surface is less than+0.3, the convex composition on the top layer obtained reduces, and the contact area on top layer increases, and release property can reduce, or the situation of the bad order on the top layer obtained.The preferred lower limit of the degree of skewness Rsk on above-mentioned surface is+0.5, and more preferably lower limit is+0.8.
In addition, the upper limit of the degree of skewness Rsk on above-mentioned surface is+1.1.When the degree of skewness Rsk on above-mentioned surface is more than 1.1, the top layer convexity composition obtained increases, and such as, during for the mobility such as epoxy adhesive or flexibility high clung body, increases, become the reason of release property reduction with the contact area of clung body.
In this description, the degree of skewness Rsk on so-called surface, refer to following value: for the surface on top layer, r.m.s. roughness is set to Rq, when the height of salient point is set to Yi, the value obtained by following formula (3), for on the occasion of time, mean that the convex composition of the average line relative to surface is many, during for negative value, mean more than being recessed into point of average line relative to surface.
Rsk = 1 / Rq 3 · 1 / n Σ i = 1 n Yi 3 - - - ( 3 )
In above-mentioned top layer, the lower limit of the steepness Rku on surface is 5.When the steepness Rku on above-mentioned surface is less than 5, the convex form on the top layer obtained becomes mild, and the contact area on top layer increases, and release property reduces.The preferred lower limit of the steepness Rku on above-mentioned surface is 6, and more preferably lower limit is 7.
In addition, the upper limit of the steepness Rku on above-mentioned surface is 11.When the steepness Rku on above-mentioned surface is more than 11, the top layer obtained becomes level and smooth, and the contact area on top layer increases, and release property reduces.
In this description, the steepness Rku on so-called surface, refers to following value: for the surface on top layer, r.m.s. roughness is set to Rq, when the height of salient point is set to Yi, the value of being tried to achieve by following formula (4), be worth larger, mean that convex form becomes sharp-pointed, and for average line, flat part increases, be worth less, mean that convex form is milder, and for average line, flat part reduces.
Rku = 1 / Rq 4 · 1 / n Σ i = 1 n Yi 4 - - - ( 4 )
In mold release film in the of the present invention 1st, in order to only observe demoulding processing layer in the region of the surface from above-mentioned top layer to thickness 50 ~ 300nm, and preference is as carried out the surface treatments such as friction treatment to above-mentioned top layer.In addition, in the mold release film of the 2nd aspect of the present invention, in order to the above-mentioned ratio relative to the face carbonyl of orientation abreast is also controlled in above-mentioned scope, in mold release film in the of the present invention 3rd, in order to give the surface configurations such as the surface roughness Rz that meets above-mentioned scope, preferred too the surface treatments such as friction treatment are carried out to above-mentioned top layer.
Above-mentioned friction treatment is not particularly limited, and the mode preferably reaching 50 ~ 500KJ with the work done ENERGY E n (KJ) represented by following formula (5) is carried out.
En＝(Ar×J)/(W×LS) (5)
In formula (5), Ar represents that friction treatment device carries out the area (m of friction treatment 2), J represents the acting amount (KJ/ minute) for the unit interval of friction treatment, and W represents by the width (m) of the film of friction treatment, and LS represents by the linear velocity of the film of friction treatment (m/ minute).
In above formula (5), above-mentioned friction treatment device carries out the Ar (m of friction treatment area 2) be the area that friction treatment device carries out the film of friction treatment.
In addition, for the acting amount J (KJ/ minute) of the unit interval for above-mentioned friction treatment, the number of times and calculating being multiplied by carried out friction treatment by the load energy of unit interval (the load energy putting on the power source of friction treatment device that friction treatment device produces by applying pressure to film) is obtained.
In addition, the width W (m) of the above-mentioned film through friction treatment refers to that friction treatment device carries out the width of the film of friction treatment.
And then above-mentioned is the speed of film by friction treatment device by the linear velocity LS of the film of friction treatment (m/ minute).
When above-mentioned work done ENERGY E n (KJ) is less than 50KJ, sometimes the region of the above-mentioned surface from above-mentioned top layer to thickness 50 ~ 300nm, fail to observe demoulding processing layer or can not the above-mentioned ratio relative to the face carbonyl of orientation abreast be controlled in above-mentioned scope or the surface configurations such as the surface roughness Rz that meets above-mentioned scope can not be given, sometimes can not give excellent release property to the mold release film obtained.When above-mentioned work done ENERGY E n (KJ) is more than 500KJ, the flexibility of the mold release film obtained reduces, or produces fold, scar equivalent damage, thus, sometimes the tracing ability for substrate surface reduces, the outflow of bonding agent when can not suppress hot forming fully.
Above-mentioned friction treatment, more preferably carries out in the mode that the upper limit of the work done ENERGY E n (KJ) represented by above formula (5) reaches 300KJ.
In above-mentioned friction treatment, the preferred lower limit of the hot strength of the fiber of the fabric that can use in the material on the surface of friction treatment material is 1.0g/d, and preferred upper limit is 5.0g/d.When the hot strength of above-mentioned fiber is less than 1.0g/d, in above-mentioned friction treatment, elongate fiber fractures sometimes, and the mold release film obtained is attached with fiber.When the hot strength of above-mentioned fiber is more than 5.0g/d, produce fold, scar equivalent damage in the mold release film sometimes obtained, the tracing ability for substrate surface reduces, the outflow of bonding agent when fully can not suppress hot forming.More preferably the upper limit of the hot strength of above-mentioned fiber is 3.0g/d.
In addition, in this description, the hot strength of so-called fiber, refers to the hot strength of the fiber that the method according to JIS-L-1095 is tried to achieve.
The preferred lower limit of the percentage elongation of above-mentioned fiber is 1%, and preferred upper limit is 30%.When the percentage elongation of above-mentioned fiber is less than 1%, in above-mentioned friction treatment, elongate fiber fractures sometimes, is attached with fiber in the mold release film obtained.When the percentage elongation of above-mentioned fiber is more than 30%, produce fold, scar equivalent damage in the mold release film sometimes obtained, the tracing ability for substrate surface reduces, the outflow of bonding agent when can not suppress hot forming fully.More preferably the upper limit of the percentage elongation of above-mentioned fiber is 29%.
In addition, in this description, the percentage elongation of so-called fiber is the stretch percentage elongation of a fiber of trying to achieve according to the method for JIS-L-1095.
As above-mentioned fiber, such as PET, artificial silk, cotton, wool, acetic acid esters etc. can be enumerated particularly.Wherein, from fold, the scar equivalent damage that can suppress further to produce mold release film owing to carrying out friction treatment, and obtain for the excellent mold release film of the tracing ability of substrate surface, and the fiber aspect being attached to mold release film can be reduced set out, preferred artificial silk, wool.
In addition, the preferred lower limit of the coefficient of friction of the fabric that can use in the material on the surface of above-mentioned friction treatment material is 0.1, and preferred upper limit is 0.8.When the coefficient of friction of above-mentioned fabrics is less than 0.1, the release property of the mold release film sometimes obtained reduces.When the coefficient of friction of above-mentioned fabrics is more than 0.8, produce fold, scar equivalent damage in the mold release film sometimes obtained, the tracing ability for substrate surface reduces, the outflow of bonding agent when can not suppress hot forming fully.More preferably the lower limit of the coefficient of friction of above-mentioned fabrics is 0.3, and more preferably the upper limit is 0.7.
In addition, in this description, the coefficient of friction of so-called fabric is the coefficient of friction of the fabric of the polycarbonate plate relative to 2mm of trying to achieve according to the method for JIS-K-7125.
The preferred lower limit of the elastic modelling quantity of above-mentioned fabrics is 0.1MPa, and preferred upper limit is 4.0MPa.When the elastic modelling quantity of above-mentioned fabrics is less than 0.1MPa, the release property of the mold release film sometimes obtained reduces.When the elastic modelling quantity of above-mentioned fabrics is more than 4.0MPa, produce fold, scar equivalent damage in the mold release film sometimes obtained, the tracing ability for substrate surface reduces, the outflow of bonding agent when can not suppress hot forming fully.More preferably the lower limit of the elastic modelling quantity of above-mentioned fabrics is 0.7MPa, and more preferably the upper limit is 3.9MPa.
In addition, in this description, the elastic modelling quantity of so-called fabric, refers to the hardness of the fabric that the method according to JIS-K-7127 is tried to achieve.
The preferred lower limit of the hot strength of above-mentioned fabrics is 1.5N/10mm, and preferred upper limit is 2.5N/10mm.When the hot strength of above-mentioned fabrics is less than 1.5N/10mm, in above-mentioned friction treatment, elongate fiber fractures sometimes, and the mold release film obtained is attached with fiber.When the hot strength of above-mentioned fabrics is more than 2.5N/10mm, produce fold, scar equivalent damage in the mold release film sometimes obtained, the tracing ability for substrate surface reduces, the outflow of bonding agent when can not suppress hot forming fully.More preferably the lower limit of the hot strength of above-mentioned fabrics is 1.6N/10mm, and more preferably the upper limit is 2.3N/10mm, and further preferred upper limit is 1.8N/10mm.
In addition, in this description, the hot strength of so-called fabric, refers to the hot strength of the fabric that the method according to JIS-K-7127 is tried to achieve.
Friction treatment device for carrying out above-mentioned friction treatment is not particularly limited, and such as, can enumerate device for grinding and processing (model YCM-150M, Mechanology Inc. of mountain county system) etc.
In the mold release film of the 2nd aspect of the present invention, polyester based resin is contained on above-mentioned top layer.In the mold release film of the 1st aspect of the present invention and the 3rd aspect of the present invention, above-mentioned top layer is not particularly limited, but preferably containing polyester based resin.
Below, describe in detail with identical item in the mold release film of the 3rd aspect for the of the present invention 1st, the 2nd.In addition, in this description, when being simply called mold release film of the present invention, any one in the mold release film of the present invention the 1st, the 2nd and the 3rd aspect is referred to.
Above-mentioned polyester based resin is not particularly limited.By using above-mentioned polyester based resin, and making the mold release film obtained show excellent mechanical performance, particularly can show excellent mechanical performance in the temperature field of about 170 DEG C carrying out usual hot forming.In addition, by using above-mentioned polyester based resin, thus environmental pressure when making the mold release film obtained carry out burning disposal is gently subtracted, also favourable economically.And then the low molecular weight compositions in above-mentioned polyester based resin is few, the non-polluting of the mold release film therefore obtained is excellent, the problem such as the plating of the electrode section of the flexible printed circuit board caused due to the oozing out of low molecular weight compositions with hot pressing can also be suppressed bad.
As above-mentioned polyester based resin, such as, preferred crystalline aromatic polyester resin.
Above-mentioned crystalline aromatic polyester resin is not particularly limited, and such as, can enumerate the crystalline aromatic polyester resin etc. making aromatic dicarboxylic acid or its ester formative derivative and low-molecular-weight aliphatic diol react and obtain.
In addition, as above-mentioned crystalline aromatic polyester resin, also can enumerate and make aromatic dicarboxylic acid or its ester formative derivative and low-molecular-weight aliphatic diol and high molecular weight diol reaction and the crystalline aromatic polyester resin (hereinafter also referred to as " there is in main chain the crystalline aromatic polyester resin of polyether skeleton ") that obtains; The crystalline aromatic polyester resin dissolves obtained making aromatic dicarboxylic acid or its ester formative derivative and the reaction of low-molecular-weight aliphatic diol is after caprolactone monomer, make caprolactone ring-opening polymerisation and the crystalline aromatic polyester resin (hereinafter also referred to as " there is in main chain the crystalline aromatic polyester resin of polycaprolactone skeleton ") etc. obtained.
Wherein, there is in use main chain the situation in the crystalline aromatic polyester resin of polyether skeleton, main chain with the crystalline aromatic polyester resin of polycaprolactone skeleton, as compared to the situation employing the crystalline aromatic polyester resin that aromatic dicarboxylic acid or its ester formative derivative react with low-molecular-weight aliphatic diol and obtain, the mold release film obtained can maintain heat resistance and have again excellent flexibility and release property, therefore preferably.
As above-mentioned aromatic dicarboxylic acid or its ester formative derivative, such as, can enumerate terephthalic acid (TPA), M-phthalic acid, phthalic acid, naphthalenedicarboxylic acid, to phenylene dicarboxylic acids, dimethyl terephthalate (DMT), DMIP, repefral, naphthalene diformic acid dimethyl ester, to phenylene dicarboxylic acids dimethyl etc.These can be used alone, and also can more than 2 kinds use.
As above-mentioned low-molecular-weight aliphatic diol, such as, ethylene glycol, 1,2-propane diol, 1 can be enumerated, 3-propane diol, 1,3-butanediol, Isosorbide-5-Nitrae-butanediol, neopentyl glycol, 1,5-pentane diol, 1,6-hexane diol, 1,4-CHDM etc.These can be used alone, and also can more than 2 kinds use.
As above-mentioned high molecular weight diol, such as, polyethylene glycol, polypropylene glycol, poly-BDO can be enumerated, poly-1,6-hexylene glycol etc.These can be used alone, and also can more than 2 kinds use.
As above-mentioned crystalline aromatic polyester resin, more specifically can enumerate, such as, PETG, polybutylene terephthalate (PBT), poly terephthalic acid hexylene glycol ester, PEN, PBN, terephthalic acid (TPA) butanediol-poly-1,4-butanediol copolymer, terephthalic acid (TPA) butanediol-polycaprolactone co-polymer etc.These can be used alone, and also can more than 2 kinds use.Wherein, from the viewpoint of the non-polluting of the mold release film obtained and crystallinity excellent especially, preferred polybutylene terephthalate (PBT).
The fusing point that above-mentioned crystalline aromatic polyester resin uses differential scanning calorimetry (DSC) to measure is preferably more than 200 DEG C.
Usually, hot forming carries out being less than under 200 DEG C of conditions, therefore by using the resin that such fusing point is high, thus the release property of melting not occurring when the mold release film obtained can have hot forming yet, can suppress destruction during hot forming.In addition, as differential scanning calorimetry (DSC), such as, DSC 2920 (TAINSTRUMENTS Inc.) etc. can be enumerated.
When the fusing point of the use differential scanning calorimetry (DSC) mensuration of above-mentioned crystalline aromatic polyester resin is less than 200 DEG C, the heat resistance of the mold release film obtained reduces, and sometimes when hot forming, melting occurs.The fusing point that the use differential scanning calorimetry (DSC) of above-mentioned crystalline aromatic polyester resin measures is more preferably more than 220 DEG C.
The fusing point that above-mentioned use differential scanning calorimetry (DSC) measures is that the crystalline aromatic polyester resin of more than 200 DEG C is not particularly limited, such as, PETG, polybutylene terephthalate (PBT), poly terephthalic acid hexylene glycol ester, PEN, PBN, terephthalic acid (TPA) butanediol-poly-BDO copolymer etc. can be enumerated.These can be used alone, and also can more than 2 kinds use.Wherein, from the view point of non-polluting and the crystallinity excellence of the mold release film obtained, preferred polybutylene terephthalate (PBT).
Stabilizing agent can be contained in above-mentioned top layer.Aforementioned stable agent is not particularly limited, such as, can enumerate hindered phenol system antioxidant, heat stabilizer etc.
Above-mentioned hindered phenol system antioxidant is not particularly limited, such as, can enumerate 1,3,5-trimethyl-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, 3, two { the 2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl)-propionyloxy)-1 of 9-, 1-dimethyl ethyl }-2,4,8,10-tetra-oxaspiro (5,5) hendecane etc.
Above-mentioned heat stabilizer is not particularly limited; such as can enumerate three (2; 4-di-tert-butyl-phenyl) phosphite ester, trilauryl phosphite, the 2-tert-butyl group-α-(3-tert-butyl-hydroxy phenyl)-to cumenyl two (to nonyl phenyl) phosphite ester, myristyl-3; 3 '-thiodipropionate, distearyl acyl group-3; 3 '-thiodipropionate, pentaerythrite four (3-lauryl thiopropionate), two (tridecyl)-3,3 '-thiodipropionate etc.
The additives such as fiber, inorganic filler, fire retardant, ultra-violet absorber, antistatic agent, inorganic matter, higher fatty acid salt, in the scope not damaging effect of the present invention, can be contained in above-mentioned top layer.
Above-mentioned fiber can be inorfil, also can be organic fiber.Above-mentioned inorfil is not particularly limited, such as, can enumerate glass fibre, carbon fiber, boron fibre, silicon carbide fibre, alumina fibre, amorphous fiber, silicon-titanium-carbon series fiber etc.Above-mentioned organic fiber is not particularly limited, such as, can enumerate aramid fibre etc.
Above-mentioned inorganic filler is not particularly limited, such as, can enumerate calcium carbonate, titanium oxide, mica, talcum etc.
Above-mentioned fire retardant is not particularly limited, such as, can enumerate HBCD, three-(2,3-bis-chloropropyl) phosphate, penta-bromophenyl allyl ethers etc.
Above-mentioned ultra-violet absorber is not particularly limited, such as, can enumerate tert-butylphenyl salicylate acid esters, ESCALOL 567,2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone, 2,4,5-trihydroxybutyrophenones etc.
Above-mentioned antistatic agent is not particularly limited, and such as, can enumerate N, N-two (hydroxyethyl) alkylamine, alkylallyl sulfonate, alkylsulfonates etc.
Above-mentioned inorganic matter is not particularly limited, such as, can enumerate barium sulfate, aluminium oxide, silica etc.
Above-mentioned higher fatty acid salt is not particularly limited, such as, can enumerate odium stearate, barium stearate, sodium palmitate etc.
Properties modifying in order to by this top layer of above-mentioned top layer, and can thermoplastic resin and rubber constituent be contained.
Above-mentioned thermoplastic resin is not particularly limited, such as, can enumerate polyolefin, improved polyalkene, polystyrene, polyvinyl chloride, polyamide, Merlon, polysulfones, polyester etc.
Above-mentioned rubber constituent is not particularly limited, such as, can enumerate natural rubber, SB, polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer (EPM, EPDM), polychlorobutadiene, butyl rubber, acrylic rubber, silicon rubber, polyurethane rubber, olefin series thermoplastic elastomer, styrene series thermoplastic elastomer, vinyl chloride thermoplastic elastomer (TPE), ester based thermoplastic elastomer, acid amides based thermoplastic elastomer etc.
The large inorganic compound of asperratio can also be contained in above-mentioned top layer.
By containing the large inorganic compound of above-mentioned asperratio, thus the release property under the high temperature of the mold release film obtained improves, and then additive, low-molecular-weight thing etc. contained in mold release film can be suppressed to ooze out to mold release film surface, and spatter property during hot forming improves.
The inorganic compound that above-mentioned asperratio is large is not particularly limited, such as, can enumerate the phyllosilicates such as clay, the lamellar composite hydrates etc. such as hydrotalcite.
The degree of crystallinity on above-mentioned top layer is preferably less than 25%.When above-mentioned degree of crystallinity is more than 25%, the tracing ability of the mold release film sometimes obtained reduces.The degree of crystallinity on above-mentioned top layer is more preferably 20 ~ 23%.
In addition, in this description, so-called degree of crystallinity, refers to the value of being tried to achieve with the peak intensity ratio of non-crystallized part by the crystalline portion obtained by X-ray diffraction method.
Heat treatment, in the scope not damaging effect of the present invention, for making the heat resistance of the mold release film obtained, dimensional stability, release property improve further, can be implemented in above-mentioned top layer.
Above-mentioned heat-treating methods is not particularly limited, such as, be preferably by film by the method between the roller that is heated to certain temperature, by the method etc. of heater heating film.
In addition, as long as more than the vitrification point of above-mentioned heat treated temperature resin contained in the above-mentioned top layers such as above-mentioned polyester based resin, below fusing point, be just not particularly limited, but preferred lower limit is 120 DEG C, and preferred upper limit is 200 DEG C.When above-mentioned heat treated temperature is less than 120 DEG C, sometimes almost can not get the effect based on heat treated raising release property.When above-mentioned heat treated temperature is more than 200 DEG C, during heat treatment, above-mentioned top layer becomes easily deformable, sometimes can not manufacture mold release film.The preferred lower limit of above-mentioned heat treated temperature is 170 DEG C, and the preferred upper limit is 190 DEG C.
The thickness on above-mentioned top layer is not particularly limited, and preferred lower limit is 5 μm, and the preferred upper limit is 20 μm.When the thickness on above-mentioned top layer is less than 5 μm, sometimes damage the intensity on above-mentioned top layer, during hot forming or the stripping of mold release film time there will be breakage.When the thickness on above-mentioned top layer is more than 20 μm, the flexibility of the mold release film obtained reduces, and the tracing ability for substrate surface reduces, the outflow of bonding agent when sometimes can not suppress hot forming fully.The preferred lower limit of the thickness on above-mentioned top layer is 10 μm, and the preferred upper limit is 15 μm.
As long as mold release film of the present invention has above-mentioned top layer, can be just monofilm, also can be the film of the multilayer of more than 2 layers.
When mold release film of the present invention is the film of multilayer, intermediate layer can be had.
Above-mentioned intermediate layer is preferably more than 60 DEG C containing the fusing point using differential scanning calorimetry (DSC) to measure and is less than the polyolefin-based resins of 130 DEG C further.
By using said polyolefins system resin, thus the intermediate layer obtained starts to start to soften near the temperature of melting at the bonding agent of cover layer, the mold release film therefore with such intermediate layer is excellent for the tracing ability of substrate surface, even if such as the flexible printed circuit board with 100 μm of such as the following trickle copper circuit spacing, also there is sufficient tracing ability, the outflow of bonding agent can be suppressed.
When the fusing point of the use differential scanning calorimetry (DSC) mensuration of said polyolefins system resin is less than 60 DEG C, in the keeping of mold release film, when atmosphere temperature reaches 50 ~ 60 DEG C, above-mentioned intermediate layer resin generation melting is oozed out, and sometimes causes adhesion.When the fusing point of the use differential scanning calorimetry (DSC) mensuration of said polyolefins system resin is more than 130 DEG C, the mold release film sometimes obtained reduces for the tracing ability of substrate surface.The fusing point that the use differential scanning calorimetry (DSC) of said polyolefins system resin measures is more preferably more than 65 DEG C less than 100 DEG C.
As said polyolefins system resin, particularly, polyethylene, low density polyethylene (LDPE), straight-chain low density polyethylene (LDPE), polypropylene, ethylene methyl methacrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer etc. can such as be enumerated.These can be used alone, and also can more than 2 kinds use.Wherein, preferred low density polyethylene (LDPE), straight-chain low density polyethylene (LDPE), ethylene methyl methacrylate copolymer, ethylene-vinyl acetate copolymer.
Above-mentioned intermediate layer is further preferably containing the resin that the fusing point using differential scanning calorimetry (DSC) to measure is more than 130 DEG C.
When using the above-mentioned fusing point utilizing differential scanning calorimetry (DSC) to measure to be more than 60 DEG C in above-mentioned intermediate layer and be less than the low resin of the softening temperature of the polyolefin-based resins of 130 DEG C and so on, due to pressure during hot forming, sometimes in the end of mold release film, resin oozes out from above-mentioned intermediate layer, printed circuit board can be polluted, heating platen etc.To this, by being the resin of more than 130 DEG C further and with the above-mentioned fusing point utilizing differential scanning calorimetry (DSC) to measure, thus the situation of oozing out resin from above-mentioned intermediate layer produced in the end of mold release film when can suppress hot forming.
The fusing point that above-mentioned use differential scanning calorimetry (DSC) measures is that the resin of more than 130 DEG C is not particularly limited, such as, can enumerate polypropylene, crystalline aromatic polyester resin etc.
When the fusing point that above-mentioned use differential scanning calorimetry (DSC) mensuration is contained in above-mentioned intermediate layer is the resin of more than 130 DEG C, the use level of such resin is not particularly limited, and the preferred lower limit in intermediate layer is 5 % by weight, and the preferred upper limit is 50 % by weight.The fusing point that above-mentioned use differential scanning calorimetry (DSC) measures is the use level of the resin of more than 130 DEG C when being less than 5 % by weight, sometimes can not be inhibited fully hot forming time the effect of oozing out resin from above-mentioned intermediate layer that occurs in the end of mold release film.The fusing point that above-mentioned use differential scanning calorimetry (DSC) measures be the use level of the resin of more than 130 DEG C more than 50 % by weight time, the mold release film sometimes obtained reduces for the tracing ability of substrate surface.
Above-mentioned intermediate layer is same with above-mentioned top layer, can contain the additives such as fiber, inorganic filler, fire retardant, ultra-violet absorber, antistatic agent, inorganic matter, higher fatty acid salt.
The thickness in above-mentioned intermediate layer is not particularly limited, but preferred lower limit is 10 μm, and the preferred upper limit is 200 μm.When the thickness in above-mentioned intermediate layer is less than 10 μm, above-mentioned intermediate layer is excessively thin, and when during hot forming, intermediate layer occurs softening, part produces the position that there is not intermediate layer sometimes, can not by squeeze pressure equably load in substrate.When the thickness in above-mentioned intermediate layer is more than 200 μm, above-mentioned intermediate layer is necessary above thickness, therefore sometimes cannot suppress the situation of oozing out resin from above-mentioned intermediate layer occurred in film end during hot forming.The preferred lower limit of the thickness in above-mentioned intermediate layer is 20 μm, and the preferred upper limit is 100 μm.
Mold release film of the present invention pressurize at 170 DEG C, with load 3MPa 60 minutes time size changing rate be preferably less than 1.5%.When above-mentioned size changing rate is more than 1.5%, sometimes during hot forming, damage the circuit pattern of flexible printed circuit board.Above-mentioned size changing rate is more preferably less than 1.0%.
In addition, for mold release film of the present invention, the width (hereinafter referred to as TD) of preferred mold release film and the size changing rate of length direction (hereinafter referred to as MD) are equidirectional and equal extent.Shrink according to one (such as MD), another (such as, TD) extends such mode, when change in size is in length and breadth different, sometimes damages the circuit pattern of flexible printed circuit board when hot forming because of mold release film.
The purposes of mold release film of the present invention is not particularly limited, such as, mold release film of the present invention preferably across prepreg or heat-resistant film by copper-clad laminated board or Copper Foil hot forming on substrate, and when manufacturing printed circuit board, flexible printed circuit board or multilayer printed-wiring board, can be used in preventing heating platen and the printed circuit board obtained, bonding with flexible printed circuit board or multilayer printed-wiring board.
In addition, mold release film of the present invention, also preferred across Thermocurable bonding agent, being adhered to by cover layer by hot forming is formed on the substrate of copper circuit, and during manufacturing flexible printed circuit board (PCB), can be used in preventing the bonding of heating platen and above-mentioned cover layer, or above-mentioned cover layer each other bonding.
And then mold release film of the present invention is also preferred when manufacturing semiconductor mould by hot forming, may be used for preventing the bonding of forming molds and resin mould.
The method manufacturing mold release film of the present invention is not particularly limited, preferably after the film masking that will there is above-mentioned top layer, above-mentioned top layer is carried out to the surface-treated methods such as friction treatment as described above, more specifically, such as be preferably as follows described method: there is the operation of with friction treatment material, the surface on above-mentioned top layer being carried out to friction treatment, the material on the surface of above-mentioned friction treatment material is be the fibroplastic fabric of 1.0 ~ 5.0g/d by hot strength, the mode reaching 50 ~ 500KJ with the work done ENERGY E n (KJ) represented by above formula (5) carries out above-mentioned friction treatment.
The film-forming method of mold release film of the present invention is not particularly limited, such as, the method be filmed with water-cooled or air-cooled type coextrusion inflation forming process, coextrusion T modulus method can be enumerated, after the above-mentioned top layer of making, utilize extruding layer platen press in the method in stacked intermediate layer, this top layer, using the method for the film as above-mentioned top layer and the film dried layer pressure as intermediate layer, solvent cast method, hot forming method etc.Wherein, when mold release film of the present invention is the film of multilayer, can by excellently control from the thickness of each layer, preferably by the method that coextrusion T modulus method is filmed.
In above-mentioned solvent cast method, such as prime coat (Japanese: ア Application カ mono-Layer) bottoming is coated on after on the film becoming intermediate layer, this prime coat is such as brushed above-mentioned polyester based resin etc. is dissolved in solvent and obtain will become the resin combination on top layer, equably film heated and make it dry, thus forming top layer.
In addition, in above-mentioned hot forming method, such as, the film becoming above-mentioned top layer is overlapped with the film becoming intermediate layer and carries out hot forming.
The effect of invention
According to the present invention, release property can be provided excellent and tracing ability for substrate surface is excellent, the mold release film of the outflow of bonding agent when can suppress hot forming.
Accompanying drawing explanation
Fig. 1 is the profile of the part on the top layer of the mold release film schematically showing the 1st aspect of the present invention.
Fig. 2 is the profile of the part on the top layer of the mold release film schematically showing the 1st aspect of the present invention.
Fig. 3 is the profile of the part on the top layer of the mold release film schematically showing the 1st aspect of the present invention.
Fig. 4 is the mold release film for obtaining in embodiment 1, utilizes transmission electron microscope to observe to use slicer to cut off and the section that obtains and the image that obtains at thickness direction.
Fig. 5 is the mold release film for obtaining in embodiment 2, utilizes transmission electron microscope to observe to use slicer to cut off and the section that obtains and the image that obtains at thickness direction.
Fig. 6 is the mold release film for obtaining in embodiment 3, utilizes transmission electron microscope to observe to use slicer to cut off and the section that obtains and the image that obtains at thickness direction.
Fig. 7 is the mold release film for obtaining in embodiment 5, utilizes transmission electron microscope to observe to use slicer to cut off and the section that obtains and the image that obtains at thickness direction.
Fig. 8 is the mold release film for obtaining in comparative example 1, utilizes transmission electron microscope to observe to use slicer to cut off and the section that obtains and the image that obtains at thickness direction.
Detailed description of the invention
Below enumerate embodiment to further describe embodiments of the present invention, but the present invention is not limited only to following examples.
In addition, in following embodiment and comparative example, be PET as the Dong Li Inc. " ToraySee " of the materials'use on the surface of friction treatment material and Supreme Being people's fiber company system " Tetoron ".
(embodiment 1)
Using polybutylene terephthalate (PBT) (the Novaduran 5010R5 of the crystalline aromatic polyester resin as top layer, Mitsubishi Engineering-Plastics Inc., fusing point 224 DEG C), as straight-chain low density polyethylene (LDPE) (the Excellen FX (CX5501) of the polyolefin-based resins in intermediate layer, sumitomo chemical company system, fusing point 66 DEG C) and ethylene methyl methacrylate copolymer (Acryft (WH401), sumitomo chemical company system, fusing point 86 DEG C) and polypropylene (PS207A, Sunallomer Inc., fusing point 160 DEG C), drop into coextrusion forming machine, T mould is utilized to carry out coextrusion shaping, obtain the thickness 10 μm on top layer, the film of the thickness 80 μm in intermediate layer.In addition, fusing point uses differential scanning calorimetry (DSC) (DSC 2920, TA INSTRUMENTS Inc.) to measure.
Use and have employed by the friction treatment device (device for grinding and processing of the fibroplastic fabric shown in table 1 as the friction treatment material of surfacing, model YCM-150M, Mechanology Inc. of mountain county system), to become the mode of the work done energy (KJ) shown in table 1, friction treatment is carried out to the surface on the top layer of the film obtained, obtains mold release film.
In addition, work done energy is by carrying out the area A r (m of friction treatment by friction treatment device 2), for the acting amount J (KJ/ minute) of the unit interval of friction treatment, by the width W (m) of the film of friction treatment be updated in formula (5) by the linear velocity LS of the film of friction treatment (m/ minute) and calculate.
For the mold release film obtained, by transmission electron microscope (TEM) (model H-9500, Hitachi's high-tech company system) observe use sliding microtome (model SM2000R, Ikeda physics and chemistry Inc.) cut off at thickness direction and obtain section time, only in the region of the surface from top layer to the thickness (nm) shown in table 1, observe demoulding processing layer.In embodiment 1, Fig. 4 illustrates the image observed by transmission electron microscope.In addition, by the peak intensity ratio of the crystalline portion obtained by X-ray diffraction method with non-crystallized part, the degree of crystallinity (%) on top layer is calculated.
(embodiment 2 ~ 5)
As shown in table 1, change material and the work done energy (KJ) on the surface of friction treatment material, in addition, obtain mold release film similarly to Example 1.
For the mold release film obtained, utilize transmission electron microscope (TEM) (model H-9500, Hitachi's high-tech company system) observe use sliding microtome (model SM2000R, Ikeda physics and chemistry Inc.) cut off at thickness direction and obtain section time, only in the region of the surface from top layer to the thickness (nm) shown in table 1, observe demoulding processing layer.The image observed by transmission electron microscope in embodiment 2 is shown in Fig. 5, and the image observed by transmission electron microscope in embodiment 3 is shown in Fig. 6, and the image observed by transmission electron microscope in embodiment 5 is shown in Fig. 7.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 1.
(comparative example 1)
Except not carrying out, except friction treatment, obtaining mold release film similarly to Example 1.
For the mold release film obtained, by transmission electron microscope (TEM) (model H-9500, Hitachi's high-tech company system) observe use sliding microtome (model SM2000R, Ikeda physics and chemistry Inc.) thickness direction cut off and obtain section time, do not observe demoulding processing layer.The image observed by transmission electron microscope is shown in Fig. 8.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 1.
(comparative example 2 ~ 3)
As shown in table 2, change material and the work done energy (KJ) on the surface of friction treatment material, in addition, obtain mold release film similarly to Example 1.
For the mold release film obtained, by transmission electron microscope (TEM) (model H-9500, Hitachi's high-tech company system) observe use sliding microtome (model SM2000R, Ikeda physics and chemistry Inc.) cut off at thickness direction and obtain section time, only in the region of the surface from top layer to the thickness (nm) shown in table 2, observed demoulding processing layer.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 1.
(embodiment 6)
Using polybutylene terephthalate (PBT) (the Novaduran 5010R5 of the crystalline aromatic polyester resin as top layer, Mitsubishi Engineering-Plastics Inc., fusing point 224 DEG C), as straight-chain low density polyethylene (LDPE) (the Excellen FX (CX5501) of the polyolefin-based resins in intermediate layer, sumitomo chemical company system, fusing point 66 DEG C) and ethylene methyl methacrylate copolymer (Acryft (WH401), sumitomo chemical company system, fusing point 86 DEG C) and polypropylene (PS207A, Sunallomer Inc., fusing point 160 DEG C), drop into coextrusion forming machine, T mould is utilized to carry out coextrusion shaping, obtain the thickness 10 μm on top layer, the film of the thickness 80 μm in intermediate layer.In addition, fusing point uses differential scanning calorimetry (DSC) (DSC 2920, TA INSTRUMENTS Inc.) to measure.
Use and have employed by the friction treatment device (device for grinding and processing of the fibroplastic fabric shown in table 3 as the friction treatment material of surfacing, model YCM-150M, Mechanology Inc. of mountain county system), to become the mode of the work done energy (KJ) shown in table 3, friction treatment is implemented to the surface on the top layer of the film obtained, obtains mold release film.
In addition, work done energy is by carrying out the area A r (m of friction treatment by friction treatment device 2), for the acting amount J (KJ/ minute) of the unit interval of friction treatment, by the width W (m) of the film of friction treatment be updated to formula (5) by the linear velocity LS of the film of friction treatment (m/ minute) and calculate.
For the region of surface to thickness 1 μm from top layer of the mold release film obtained, use film evaluation sample horizontal type X-ray diffraction device (model Smart Lab, society of science system) carry out X-ray parsing, obtain the ratio (%) relative to the face carbonyl of orientation abreast.
In addition, relative to face abreast the carbonyl of orientation ratio (%) by resolved by X-ray obtain relative to face abreast the carbonyl of orientation peak intensity A and relative to face vertically the carbonyl of orientation peak intensity B substitute into formula (1) calculate.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 1.
(embodiment 7 ~ 9)
As shown in table 3, change material and the work done energy (KJ) on the surface of friction treatment material, in addition, obtain mold release film similarly to Example 6.
For the region of surface to thickness 1 μm from top layer of the mold release film obtained, use film evaluation sample horizontal type X-ray diffraction device (model Smart Lab, society of science system) carry out X-ray parsing, obtain the ratio (%) relative to the face carbonyl of orientation abreast.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 6.
(comparative example 4)
Except not carrying out, except friction treatment, obtaining mold release film similarly to Example 6.
For the region from surface to thickness 1 μm on the top layer of the mold release film obtained, use film evaluation sample horizontal type X-ray diffraction device (model Smart Lab, society of science system) carry out X-ray parsing, obtain the ratio (%) relative to the face carbonyl of orientation abreast.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 6.
(embodiment 10)
Using polybutylene terephthalate (PBT) (the Novaduran 5010R5 of the crystalline aromatic polyester resin as top layer, Mitsubishi Engineering-Plastics Inc., fusing point 224 DEG C), and straight-chain low density polyethylene (LDPE) (the Excellen FX (CX5501) of polyolefin-based resins as intermediate layer, sumitomo chemical company system, fusing point 66 DEG C) and ethylene methyl methacrylate copolymer (Acryft (WH401), sumitomo chemical company system, fusing point 86 DEG C) and polypropylene (PS207A, Sunallomer Inc., fusing point 160 DEG C), drop into coextrusion forming machine, T mould is utilized to carry out coextrusion shaping, obtain the thickness 10 μm on top layer, the film of the thickness 80 μm in intermediate layer.In addition, fusing point uses differential scanning calorimetry (DSC) (DSC 2920, TA INSTRUMENTS Inc.) to measure.
Use friction treatment device (model YCM-150M, Mechanology Inc. of mountain county system), to become the mode of the work done energy (KJ) shown in table 4, by the fabric that will be formed by the cotton friction treatment material as surfacing, friction treatment is carried out to the top layer of the film obtained, the surface roughness Rz obtaining top layer is thus 250nm, and the degree of skewness Rsk on surface is+0.80, and the steepness Rku on surface is the mold release film of 8.In addition, the surface roughness Rz on top layer, degree of skewness Rsk and the surperficial steepness Rku on surface use above formula (2) respectively, (3) and (4) calculate.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 1.
(embodiment 11)
As shown in table 4, change work done energy (KJ), in addition, similarly to Example 10, the surface roughness Rz obtaining top layer is 250nm, and the degree of skewness Rsk on surface is+0.30, and the steepness Rku on surface is the mold release film of 5.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 10.
(embodiment 12)
As shown in table 4, change work done energy (KJ), replace the fabric that formed by the cotton friction treatment material as surfacing, but utilize the fabric formed by wool is carried out friction treatment as the friction treatment material of surfacing, in addition, similarly to Example 10, the surface roughness Rz obtaining top layer is 380nm, the degree of skewness Rsk on surface is+0.85, and the steepness Rku on surface is the mold release film of 7.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 10.
(embodiment 13)
Replace the fabric that formed by the cotton friction treatment material as surfacing, but utilize the fabric formed by wool is carried out friction treatment as the friction treatment material of surfacing, in addition, similarly to Example 10, the surface roughness Rz obtaining top layer is 430nm, the degree of skewness Rsk on surface is+1.10, and the steepness Rku on surface is the mold release film of 11.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 10.
(comparative example 5)
Except not carrying out except friction treatment, similarly to Example 10, the surface roughness Rz obtaining top layer is 200nm, and the degree of skewness Rsk on surface is+0.50, and the steepness Rku on surface is the mold release film of 3.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 10.
(comparative example 6)
As shown in table 4, change work done energy (KJ), replace the fabric that formed by the cotton friction treatment material as surfacing, but utilize the fabric formed by PET is carried out friction treatment as the friction treatment material of surfacing, in addition, similarly to Example 10, the surface roughness Rz obtaining top layer is 258nm, the degree of skewness Rsk on surface is-0.34, and the steepness Rku on surface is the mold release film of 3.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 10.
(comparative example 7)
As shown in table 4, change work done energy (KJ), replace the fabric that formed by the cotton friction treatment material as surfacing, but utilize the fabric formed by PET is carried out friction treatment as the friction treatment material of surfacing, in addition, similarly to Example 10, the surface roughness Rz obtaining top layer is 280nm, the degree of skewness Rsk on surface is+0.29, and the steepness Rku on surface is the mold release film of 3.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 10.
(comparative example 8)
As shown in table 4, change work done energy (KJ), replace the fabric that formed by the cotton friction treatment material as surfacing, but utilize the fabric formed by wool is carried out friction treatment as the friction treatment material of surfacing, in addition, similarly to Example 10, the surface roughness Rz obtaining top layer is 240nm, the degree of skewness Rsk on surface is+0.25, and the steepness Rku on surface is the mold release film of 4.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 10.
(comparative example 9)
As shown in table 4, change work done energy (KJ), replace the fabric that formed by the cotton friction treatment material as surfacing, but utilize the fabric formed by wool is carried out friction treatment as the friction treatment material of surfacing, in addition, similarly to Example 10, the surface roughness Rz obtaining top layer is 460nm, the degree of skewness Rsk on surface is+1.15, and the steepness Rku on surface is the mold release film of 12.In addition, the degree of crystallinity (%) on top layer is calculated similarly to Example 10.
(evaluation)
For the mold release film obtained in embodiment, comparative example, carry out following evaluation.Result is as shown in table 1 ~ 4.
(1) release property (peeling force)
Square cover layer (the CISV-2535 of 200mm will be cut into, NIKKAN industrial group system) epoxy adhesive face, overlapping with the face, top layer of the mold release film obtained, use slidingtype vacuum hotpressing machine (MKP-3000v-MH-ST, MIKADO TECHNOS Inc.), with pressure 30kgf, 180 DEG C, after the extruding of carrying out 6 minutes, with 23 DEG C, the condition of 50%RH carries out the health of 1 day.Subsequently, the evaluation sample of width 30mm, length 150mm is cut out by the sample after health, for this evaluation sample, use Tensilon (STA-1150, A & D Inc.), with peeling rate 500mm/ minute, peel angle 180 ° measure peeling force (N/30mm).
(2) tracing ability (imbedibility)
Copper-clad laminated board (20cm × 20cm is stacked gradually from beneath, thick polyimide 25 μm, Copper Foil 18 μm, hereinafter referred to as " CCL "), cover layer (20cm × 20cm, thick polyimide 12 μm, epoxy system resin bond layer 15 μm) and the mold release film that obtains, utilize vacuum press, at 160 DEG C, 30kg/cm 2, extrude under the condition of 30 minutes, make the FPC comprising CCL and cover layer and evaluate sample.In addition, for cover layer, the model (200 μm of intervals, 100 μm of intervals) of bonding agent discharge evaluation is made in advance.
Subsequently, take out FPC and evaluate sample and mold release film, with the hole of the bonding agent discharge evaluation on microscopic examination cover layer, measure the length of the bonding agent flowed out.When the length of bonding agent flowed out is less than 10 μm, be designated as ◎, be more than 10 μm and be designated as zero when being less than 20 μm, be more than 20 μm and be designated as △ when being less than 30 μm, be designated as when more than 30 μm ×, evaluate thus.
[table 1]
[table 2]
[table 3]
[table 4]
Industry utilizes possibility
According to the present invention, release property can be provided excellent and tracing ability for substrate surface is excellent, the mold release film of the outflow of bonding agent when can suppress hot forming.
Symbol description
1 demoulding processing layer
2,2 ', 2 " other regions in top layer

Claims (5)

1. a mold release film, is characterized in that, is the mold release film on the top layer had containing polyester based resin, wherein,
In the region of the surface from described top layer to thickness 1 μm, use X-ray resolver mensuration relative to the diffraction of the X-ray of the surperficial oblique incidence of described mold release film, A is set as relative to the peak intensity of the surperficial carbonyl of orientation abreast of mold release film by what record, by record be set as B relative to the peak intensity of the mold release film surface vertically carbonyl of orientation time
Be more than 45% relative to the ratio X of the mold release film surface carbonyl of orientation abreast in carbonyl contained the region of the surface from described top layer calculated according to following formula (1) to thickness 1 μm,
X＝{A/(A+B)}×100％ (1)。
2. mold release film as claimed in claim 1, it is characterized in that, the degree of crystallinity on top layer is less than 25%.
3. mold release film as claimed in claim 1 or 2, it is characterized in that, across prepreg or heat-resistant film, when copper-clad laminated board or Copper Foil hot forming being manufactured printed circuit board, flexible printed circuit board or multilayer printed-wiring board in substrate, for preventing the bonding of heating platen and obtained printed circuit board, flexible printed circuit board or multilayer printed-wiring board.
4. mold release film as claimed in claim 1 or 2, it is characterized in that, across Thermocurable bonding agent, when cover layer being adhered to by hot forming the substrate and manufacturing flexible printed circuit board (PCB) that are formed with copper circuit, for preventing heating platen and the bonding of described cover layer or described cover layer each other bonding.
5. mold release film as claimed in claim 1 or 2, is characterized in that, when manufacturing semiconductor mould by hot forming, can be used in preventing the bonding of forming molds and resin mould.
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