CN101346665B - Surface-protective film - Google Patents

Surface-protective film Download PDF

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Publication number
CN101346665B
CN101346665B CN2006800493962A CN200680049396A CN101346665B CN 101346665 B CN101346665 B CN 101346665B CN 2006800493962 A CN2006800493962 A CN 2006800493962A CN 200680049396 A CN200680049396 A CN 200680049396A CN 101346665 B CN101346665 B CN 101346665B
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China
Prior art keywords
resin
condensation reaction
reaction type
sealer
fissility
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CN2006800493962A
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CN101346665A (en
Inventor
梶谷邦人
今村顺一
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Kimoto Co Ltd
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Kimoto Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin 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
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/14Production of collotype printing forms
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20Exposure; Apparatus therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20Exposure; Apparatus therefor
    • G03F7/2002Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2014Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/412Transparent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/748Releasability
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/08PCBs, i.e. printed circuit boards
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

Abstract

A surface-protective film which comprises a transparent polymer film, a pressure-sensitive adhesive layer formed on one side thereof, and a surface-protective layer formed on the other side, wherein the surface-protective layer is formed from a release ingredient comprising a condensation reaction type silicone resin having a contact angle with water as measured according to JIS R3257:1999 of 100 DEG or larger and a binder ingredient comprising a condensation reaction type resin having a contact angle with water as measured according to JIS R3257:1999 of 90 DEG or smaller. Preferably the condensation reaction type resin having a contact angle with water as measured according to JIS R3257:1999 of 90 DEG or smaller comprises a condensation reaction type silicone resin. This surface-protective film can retain extremely high releasability from photoresists.

Description

Surface protective film
Technical area
The present invention relates to a kind of surface protective film, particularly relate to a kind of surface protective film that is suitable in printed circuit board production process etc. surface with adhesive photoresist original copy (photo etched mask) when exposing with fissility.
Background technology
Usually, printed wiring board or resin relief are by having adhesive photoresist and adhere to and exposure photo-etching mask (exposure original copy) being made to aqueous photoresist etc.Therefore, if do not carry out some processing, after then exposure is on the photo etched mask surface, from photoresist stripping photolithography mask the time, photoresist partly will be attached to the photo etched mask surface, even wiping, still can remain on the mask, generation is caused the bad problem of exposure accuracy.Because above-mentioned reason, the one side with respect to photoresist on photo etched mask is provided with the surface protection film with fissility all the time, prevents that photoresist is attached to the situation on the photo etched mask.
As the surface protective film that this photo etched mask is used, the one side that has been proposed in plastic sheeting possesses the sealer with fissility, and has the film (patent documentation 1) of adhesive coating at another side.As the material that constitutes sealer, use silicone resin etc. to have the resin of fissility usually.
Even yet at this surface protective film; can not prevent fully that photoresist is attached to sealer; whenever when the sealer repetitiousness exposes; because of the photoresist that all adheres on a small quantity at every turn; problems such as light crested when causing exposing or increase light scattering, the obstruction when perhaps becoming exposure.In addition, the concave-convex surface of the photoresist that adheres to is transferred on the substrate (resist), become because of damage cause bad.
In order to solve such problem, also, need use cleaning solvent to clean the surface of (wiping operation) surface protection film termly in order to remove the photoresist and other dusts or the like that remains on the surface protection film.(patent documentation 2)
Yet this operation is quite loaded down with trivial details, and in order to improve output, wishes to reduce cleaning time or save cleaning process.
Patent documentation 1: the spy opens flat 11-7121 communique (technical scheme)
Patent documentation 2: the spy opens 2003-96409 communique (problem that the invention desire solves)
Summary of the invention
Therefore the objective of the invention is to, a kind of surface protective film with respect to the sustainable high fissility of photoresist is provided.
In order to realize described problem, the research back is found, when the repetitiousness exposing operation, all can adhere to a small amount of photoresist on the surface protection film, thereby the fissility of surface protection film is lost gradually.
Therefore; inventors of the present invention; in order to realize such purpose; the result who concentrates on studies; discovery contains as among the JIS R3257:1999 of fissility composition and contact angle water by utilization and is the above condensation reaction type silicone resin of 100 degree and is that the following condensation reaction type resin of 90 degree constitutes surface protection film as among the JIS R3257:1999 of adhesive ingredients and contact angle water; promptly can solve above-mentioned problem, so that finish the present invention.
That is to say; surface protective film of the present invention is the surface protective film that is provided with sealer in the one side of transparent polymer film; it is characterized in that; it is the above condensation reaction type silicone resins of 100 degree that sealer contains as among the JIS R3257:1999 of fissility composition and contact angle water, and to contain as among the JIS R3257:1999 of adhesive ingredients and contact angle water be the following condensation reaction type resins of 90 degree.
In addition, being characterized as of surface protective film of the present invention: as described and contact angle water is the following condensation reaction type resins of 90 degree, contains condensation reaction type silicone resin.
In addition, being characterized as of surface protective film of the present invention: described and contact angle water be the above resinoid ratio of condensation reaction type silicone of 100 degree with respect to described adhesive ingredients 100 weight portions, be 1 weight portion~40 weight portions.
In an embodiment of surface protective film of the present invention, be provided with adhesive coating at the another side of transparent polymer film.
In addition, sealer of the present invention is characterized as with composition, contains: among the JIS R3257:1999 and contact angle water are the above condensation reaction type silicone resins of 100 degree; With among the JISR3257:1999 and contact angle water be the following condensation reaction type resins of 90 degree.
In addition, in the surface protection film composition of the present invention, it is the following condensation reaction type silicone resins of 90 degree that described condensation reaction type resin contains among the JIS R3257:1999 and contact angle water.In surface protection film composition of the present invention, condensation reaction type resin for example contains: this condensation reaction type silicone resin that 15 weight % are above and 70 weight % are following.
Can prevent photoresist attached to surface protection film according to the present invention,, also can keep high degree fissility photoresist even do not clean.
Embodiment
Sealer of the present invention composition and surface protective film then are described.
Sealer composition of the present invention is that the contact angle that contains with water is the above condensation reaction type silicone resins of 100 degree, and with the contact angle of water be the composition of the following condensation reaction type resin of 90 degree.Sealer of the present invention can be used for forming with composition: be provided with the sealer of the surface protective film of sealer at base materials such as macromolecule membranes, and be set directly at should protect the surface material (for example: lip-deep surface protection film photo etched mask).
Surface protective film of the present invention is that the one side at the transparent polymer film is provided with sealer, and another side is provided with the surface protective film of adhesive coating, and surface protective film is formed with composition by sealer of the present invention.Below, with the embodiment of the relevant surface protective film of the present invention of explanation.
As the transparent polymer film, as long as for the high film of employed ultraviolet penetrance of when exposure both can, can use the outstanding macromolecule membranes of the transparency such as polyethylene terephthalate, polybutylene terephthalate, PEN, polycarbonate, tygon, polypropylene, polystyrene, triacetyl cellulose, acrylic acid, Polyvinylchloride.Physical strength, the dimensional stability of especially biaxial stretch-formed pet film are outstanding, therefore are particularly suitable for using.In addition, the film that suitable easy adhesive linkage etc. forms being set on these transparent polymer films also is extensive use of.
The thickness of transparent polymer film, because can have influence on the exploring degree, so get over Bao Yuehao, but consider operability, the following of thickness is limited to more than the 1 μ m, is preferably more than the 2 μ m, more preferably more than the 4 μ m, be limited on it below 100 μ m, be preferably below the 25 μ m, and then be preferably the following scope of 12 μ m.
Be arranged on the transparent polymer film with the face opposing face that is provided with sealer on adhesive coating, can use acrylic compounds sticker, the rubber-like sticker of general use, known clear binders such as carbamates sticker, silicone sticker.Surface protective film of the present invention, because purpose is to protect image etc., so bonding agent is preferably transparent, and itself has very high weatherability.As this sticker, the sticker of the acrylic compounds of the high molecular of preferred carbamate bridging property or epoxy cross-linking.In addition, also can use the sticker that possesses performances such as electrostatic prevention.
Perhaps also can adhesive coating be set in the one side of the transparent polymer film that is provided with antistatic backing.
In order not hinder the transparency (exploring degree), and can obtain appropriate stickability, the following of thickness as adhesive coating is limited to more than the 0.5 μ m, be preferably more than the 1 μ m, the above scope of 2 μ m more preferably, be limited on it below 30 μ m, be preferably below the 15 μ m, and then be preferably the following scope of 7 μ m.
In addition, reduce because of its stickability makes the operability of surface protective film, also can implement the stripping film of lift-off processing aptly at the adhesive coating coating surface in order not allow.
Be arranged on another surperficial sealer of transparent polymer film, constitute, and constitute by fissility composition and adhesive ingredients by sealer with fissility.
The fissility composition is the composition of giving for the high fissility of photoresist, is that the above condensation reaction type silicone resin of 100 degree (following also claim high contact angle condensation reaction type resin) constitutes by among the JISR3257:1999 and contact angle water mainly.In addition, adhesive ingredients is the composition of giving for the high cementability of transparent polymer film, is that the following condensation reaction type resin of 90 degree (following also claim low contact angle condensation reaction type resin) constitutes by among the JIS R3257:1999 and contact angle water mainly.
Use contains the sealer composition of these two kinds of condensation reaction type resins; when on base material, forming sealer; in the process of dried coating film, high contact angle condensation reaction type resin can be face side with restraining oneself partially, and low contact angle condensation reaction type resin then can be the base material side partially.The fissility composition carries out condensation reaction with adhesive ingredients and combines on both interfaces.Thus, by using the condensation reaction type resin of above-mentioned two kinds, at the surface protection laminar surface, the fissility composition high concentration ground that possesses high fissility exists, and therefore can obtain high fissility.In addition, because the zone that the zone that fissility composition high concentration ground exists and adhesive ingredients high concentration ground exist, can be because the condensation reaction of the resin of formation two compositions and combination, so the fissility composition can not peel off from filming, and can keep fissility.
On the other hand, only can't obtain fissility by low contact angle condensation reaction type resin as adhesive ingredients.In addition, if having only high contact angle condensation reaction type resin as the fissility composition, it is not good with the cementability between the transparent polymer film, and mechanicalness intensity is also poor in addition, and the mar resistance when contacting with printed circuit board is deficiency also.In addition, under with the situation of high contact angle condensation reaction type silicone resin as the resin combination of adhesive ingredients and non-condensation reaction type resin, perhaps will hang down under the situation of contact angle condensation reaction type resin as fissility composition and the resinoid resin combination of non-condensation reaction type silicone, because fissility composition and adhesive ingredients can't be in conjunction with, the therefore fissilities that can't obtain to continue.
Condensation reaction type silicone resin is for possessing the silicone resin as shown in the formula the siloxane main chain of (1), comprise: as the organo-functional group R and/or the terminal groups of side chain, the water-disintegrable base that generates silanol group is the silanol group (Si-OH) of regenerating after the hydrolysis, and then dehydrating condensation and form the group of siloxane bond between main chain; With the hydrophobicity base.As water-disintegrable base, can enumerate for example acetate, oximido, methoxyl, amide group, propenyloxy group etc.In addition, as the hydrophobicity base, can enumerate as phenyl, alkyl, fluorinated alkyl etc.Import water-disintegrable base and the hydrophobicity base that these constitute organo-functional group R by suitable the selection, can adjust the contact angle of the resinoid and water of condensation reaction type silicone.Specifically, the ratio of hydrophobicity base is high more can enlarge contact angle more.Reduce the ratio of hydrophobicity base in addition, increase water-disintegrable base, then can dwindle contact angle more.
[changing 1]
Figure S2006800493962D00051
Condensation reaction type silicone resin as high contact angle, for example can use: resin that dimethyl polysiloxane is had phenyl, alkyl, fluorinated alkyl as the side chain and/or the terminal groups of base polymer etc., from the viewpoint of condensation reaction, can use and contain the water-disintegrable base resin of acetate, oximido, methoxyl, amide group, propenyloxy group etc. for example that generates silanol group.
As the fissility composition, in the scope that does not hinder the function of filming, can add above-mentioned condensation reaction type silicone resin fissility composition in addition.As other fissility compositions, for example, can enumerate at side chain or terminal groups and do not have water-disintegrable silicone oil (dimethyl polysiloxane) etc.When adding other fissility compositions, condensation reaction type silicone resin in the fissility composition shared ratio preferably more than 90%.
Low contact angle condensation reaction type resin is to play a role as adhesive ingredients, use its with the contact angle of water below 90 degree, preferably at 85 resins below spending.About low contact angle condensation reaction type resin, also can constitute as the ratio of the water-disintegrable base of the organo-functional group of side chain and hydrophobicity base and adjust contact angle between condensation reaction type resin and the water by suitable adjustment.As this resinoid, can use condensation reaction type silicone resin, condensation reaction type alkyd resin, condensation reaction type melamine resin, condensation reaction type acryl resin, condensation reaction type vibrin etc.
Especially, condensation reaction type silicone resin, because of good with the resinoid intermiscibility of the silicone of fissility composition under solution state, thus preferred, for example can use resin with the water-disintegrable base that generates silanol group.In addition, the lower limit of the silicone composition that contains in condensation reaction type resin (silicone resin) is preferably more than the 15 weight %, and the upper limit is preferably about 70 weight %.By being controlled in such scope, can make as other condensation reaction type resins of adhesive ingredients and high contact angle condensation reaction type silicone interlaminar resin as the fissility composition, across as the condensation reaction type silicone resin of adhesive ingredients and mutually combine, therefore can improve and the cementability of transparent macromolecule membrane, so give sufficient curable to filming or with respect to photoresist in the sufficient mechanical and the mar resistance of the solvent that contains.
In the scope that does not hinder the function of filming, can also add in addition as the resin beyond the condensation reaction type resin of adhesive ingredients.As the resin beyond the condensation reaction type resin, for example can enumerate thermoplastic acrylic resin, thermoplastic epoxy etc.For the ratio of the condensation reaction type resin in whole adhesive ingredients, as under be limited to more than the 70 weight % about.
As the condensation reaction type silicone resin of fissility composition, with respect to adhesive ingredients 100 weight portions, its upper limit is preferably below 40 weight portions, and then is preferably below 20 weight portions, and its lower limit is preferably more than 1 weight portion, and then is preferably more than 2 weight portions.Lower limit is made as more than 1 weight portion, is because if be less than 1 weight portion, then will be difficult to obtain to peel off effect.In addition, the upper limit is made as below 40 weight portions, be because if more than 40 weight portions, then will be difficult to obtain sufficient mechanical and mar resistance for the solvent that is included in the photoresist, with the cementability variation of transparent macromolecule membrane, even and many interpolations can not improve the effect of fissility.
With in the composition, also can contain the catalyzer that is useful on the condensation reaction between promotion and above-mentioned high contact angle condensation reaction type silicone resin and the low contact angle condensation reaction type resin at sealer of the present invention.As catalyzer, can use metal fatty acid salt, known catalyzer such as metal alkoxide.Particularly, can use tin compound, zirconium compounds, titanium sub-group compound etc.
Surface protective film of the present invention; can make each composition combination by condensation reaction, can improve physical strength, mar resistance thus, perhaps reduce fissility composition coming off on film; just reduce the transfer printing of fissility composition on the printed circuit board, and improve and peel off continuation.
In sealer, concavo-convex in order to form at sealer, except that these resins, can also add particulates such as inorganic pigment or resin particle etc.As this particulate, can use lime carbonate, magnesium carbonate, barium sulphate, silica, aluminium hydroxide, porcelain earth, clay, inorganic pigments such as talcum, or acryl resin particle, styrene resin beads, urethane resin particle, polyvinyl resin particle, benzene guanamine resin particle, resin particles such as epoxy resin particle.The addition of these particulates, because of the kind of particulate, the thickness of sealer and difference can't be lumped together, but account for usually about 0.05 weight %~9.5 weight % in all solids composition that constitutes sealer.In addition, the mean grain size of this particulate, different because of the thickness of sealer, can't lump together, but be generally about 0.1 μ m~10 μ m, preferably use the particulate of 0.5 μ m~5 μ m.Concavo-convex by such formation, the suitable gap with photoresist can be set, make when adhering to exposure to remove empty ability good, and then produce neutral ring can prevent to adhere to exposure the time.
Thickness as sealer; though be not particularly limited; the low viewpoint of exploring degree of photomask when but never making exposure; preferred thickness is thin; in addition, from the skin hardness of sealer, adhere to exposure and the reduction of the sealer that causes repeatedly, the viewpoint such as continue of the fissility at initial stage and fissility is set out; particularly thickness is 0.2 μ m~5 μ m, is preferably 0.4 μ m~2.5 μ m.
With regard to aforesaid sealer or adhesive coating; cooperate each constituent or other required compositions; make it be dissolved or dispersed in preparation coating fluid in the appropriate solvent; and this coating fluid passed through rolling method; rod is coated with method; spraying process, known method such as air knife knife coating are coated on the transparent macromolecule membrane, and dry back is used appropriate necessary curing that it is solidified and is formed.
Utilize present embodiment as mentioned above, by at the member of desire protection across the adhesive coating coating surface, can easily form surface protection film.In addition, in the film skin hardness that keeps surface protection film, do not make it be stained with spot, therefore can keep high fissility for photoresist.
In addition, as surface protective film, as above embodiment illustrated as, be generally and have the adhesive coating film, but in surface protective film of the present invention, and nonessential adhesive coating, do not have the film of adhesive coating to be contained among the present invention yet.
Embodiment
Further specify the present invention by the following examples.In addition, short of dated especially, " part ", " % " are weight basis.
[embodiment 1]
With the sealer of following composition with coating fluid by rod be coated with method be coated on the transparent polymer film that thickness is 6 μ m (REMIRROR: surface Dong Li company), 120 ℃ down heating it is solidified, form the sealer that thickness is about 1 μ m.And be coated with the adhesive coating coating fluid of following composition at another side, dry back forms the adhesive coating that thickness is about 2 μ m, makes surface protective film.Be handled easily on adhesive coating, coating thickness is the polyethylene terephthalate stripping film (MRB: Mitsubishi Chemical mylar company) of 25 μ m.
<sealer coating fluid 〉
4 parts of condensation reaction type silicone resins
(KS705F: SHIN-ETSU HANTOTAI's chemical industry, contact angle 108 degree: solid constituent 30%)
60 parts of condensation reaction type silicone resins
(organosilane condensation product: melamine resin: alkyd resin=10: 3: 7, contact angle 80 degree: solid constituent 30%)
Tin is 0.5 part of curing catalysts
0.1 part of pigment
(Nipsil SS-15: eastern Cao (bundle ソ one) silica)
20 parts of methyl ethyl ketones
20 parts of toluene
<adhesive coating coating fluid 〉
10 parts of acrylic ester copolymerization things
(AKONTACK SCL-200: solid constituent 40%, East Asia synthetic chemistry)
10 parts of toluene
10 parts in ethyl acetate
[embodiment 2]
Except the sealer coating fluid with embodiment 1 is replaced with following sealer coating fluid, adopt the method identical to make surface protective film with embodiment 1.
<sealer coating fluid 〉
12 parts of condensation reaction type silicone resins
(KS705F: SHIN-ETSU HANTOTAI's chemical industry, contact angle 108 degree: solid constituent 30%)
60 parts of condensation reaction type silicone resins
(organosilane condensation product: melamine resin: alkyd resin=10: 3: 7, contact angle 80 degree: solid constituent 30%)
Tin is 0.5 part of curing catalysts
0.1 part of pigment
(Nipsil SS-15: eastern Cao's silica)
16 parts of methyl ethyl ketones
16 parts of toluene
[embodiment 3]
Except the sealer coating fluid with embodiment 1 is replaced with following sealer coating fluid, adopt the method identical to make surface protective film with embodiment 1.
<sealer coating fluid 〉
21 parts of condensation reaction type silicone resins
(KS705F: SHIN-ETSU HANTOTAI's chemical industry, contact angle 108 degree: solid constituent 30%)
60 parts of condensation reaction type silicone resins
(organosilane condensation product: melamine resin: alkyd resin=10: 3: 7, contact angle 80 degree: solid constituent 30%)
Tin is 0.5 part of curing catalysts
0.1 part of pigment
(Nipsil SS-15: eastern Cao's silica)
12 parts of methyl ethyl ketones
12 parts of toluene
[comparative example 1]
Except the sealer coating fluid with embodiment 1 is replaced with following sealer coating fluid, adopt the method identical to make surface protective film with embodiment 1.
<sealer coating fluid 〉
30 parts of polyaddition type silicone resins
(LTC750A: eastern beautiful DOW CORNING silicon (East レ ダ ウ コ one ニ Application グ シ リ コ one Application), more than contact angle 100 degree: solid constituent 30%)
0.3 part of platinum group curing catalysts
0.05 part of pigment
(Nipsil SS-15: eastern Cao's silica)
70 parts of toluene
[comparative example 2]
Except the sealer coating fluid with embodiment 1 is replaced with following sealer coating fluid, adopt the method identical to make surface protective film with embodiment 1.
<sealer coating fluid 〉
30 parts of condensation reaction type silicone resins
(KS705F: SHIN-ETSU HANTOTAI's chemical industry, more than contact angle 100 degree)
Tin is 0.6 part of curing catalysts
0.05 part of pigment
(Nipsil SS-15: eastern Cao's silica)
70 parts of toluene
For embodiment 1~3, and the surface protective film that obtains in the comparative example 1~2, estimate by following test, that is, expose by repetitiousness and to confirm to make sealer to continue to have high fissility.In addition, keep high fissility to estimate the infringement of its polyvalent alcohol equal solvent that whether is not subjected in the photoresist to be contained to photoresist.In addition, also estimate with regard to the mar resistance of sealer, evaluation result is as shown in table 1.
The evaluation of<initial stage fissility 〉
One side at the sealer of surface protective film with embodiment 1~3 and comparative example 1~2; the fit adhesion zone (NICHIBAN cello tapeNo.405:NICHIBAN company) of wide 18mm is with cupping machine (TENSILON HTM-100: be determined at 180 ° of peeling forces under the peeling rate of 300mm/min Japan Baldwin company).Be expressed as " ◎ " of measurement result less than 50g/18mm, 50g/18mm~less than be expressed as " zero " of 200g/18mm, 200g/18mm is above is expressed as " * ".
The evaluation of the fissility the during exposure of<repetitiousness 〉
As photoresist (photoresist), use ethoxylated bisphenol a diacrylate (A-BPE4: Xin Zhong village chemistry), to wherein adding the acetophenone of 3 weight % as Photoepolymerizationinitiater initiater again is optical free radical polymerization initiator (Irgacurel 84:Ciba Specialty Chemicals company), be coated with machine with rod then and on mylar, be coated with the described material that obtains, so that coating thickness becomes 10 μ m, thereby make test film A.Make the photoresist coated face of this test film A; adhere to each other with the one side of the sealer of surface protective film with embodiment 1~3 and comparative example 1~2; from the back side of one side, use metal halide lamp to carry out 200mJ/cm with sealer 2Ultraviolet exposure after, disbonded test sheet A.After same operation is carried out 100 times; one side at surface protective film with sealer; the fit adhesion zone (NICHIBAN cellotape No.405:NICHIBAN company) of wide 18mm is with cupping machine (TENSILON HTM-100: be determined at 180 ° of peeling forces under the peeling rate of 300mm/min Japan BALDWIN company).Measurement result is less than be expressed as " ◎ " of 50g/18mm, 50g/18mm~less than be expressed as " zero " of 200g/18mm, and 200g/18mm is above is expressed as " * ".
<mar resistance evaluation 〉
For the face of the sealer of the surface protective film with embodiment 1~3 and comparative example 1~2, with oozing the gauze that contains the propylene glycol monomethyl ether, the limit applies 100g/cm 2Load, reciprocal 20 times friction is carried out on the limit, then the face with sealer is observed.Being expressed as of variation " ◎ " that does not have sealer, the wiping vestige is arranged but sealer do not come off be expressed as " zero ", sealer is some come off be expressed as " △ ", sealer has be expressed as " * " that obviously comes off.
[table 1]
The initial stage fissility is estimated According to the fissility evaluation of exposure repeatedly Mar resistance is estimated
Embodiment 1
Embodiment 2
Embodiment 3
Comparative example 1 × ×
Comparative example 2 ×
Because among the embodiment 1~2; fissility composition, adhesive ingredients all form sealer with condensation reaction type silicone resin; so fissility in the early stage; in the fissility of repetitiousness exposure, arbitrary evaluation in the mar resistance, all shown to have enough performances as surface protective film.Among the embodiment 3, the fissility at initial stage, have good result in the same manner, but contain more fissility composition owing to comparing with other embodiment according to fissility and other embodiment of repetitiousness exposure, thus its mar resistance a little a little less than.
In comparative example 1, owing to used employed polyaddition type silicone resin in surface protective film in the past, therefore when the evaluation of the fissility that carries out exposing according to repetitiousness, its performance obviously descends.
In comparative example 2; because of only using the condensation reaction type silicone resin as the fissility composition to form surface protection film, so the mar resistance of sealer is obviously poor, sealer is impaired easily; therefore cause easily that the exposure of trace hinders due to wound, be not durable.

Claims (7)

1. surface protective film, it is the surface protective film that is provided with sealer in the one side of transparent polymer film, it is characterized in that,
Described sealer is formed by the solidfied material of coating composition; this coating composition has fissility composition and adhesive ingredients; described fissility composition comprises the condensation reaction type silicone resin that the contact angle with water that generates among the JIS R3257:1999 becomes the above solidfied material of 100 degree; described adhesive ingredients comprises the condensation reaction type resin that the contact angle with water that generates among the JIS R3257:1999 becomes the following solidfied material of 90 degree
And; non-base material side at described sealer is that face side high concentration ground exists from the resinoid first area of described condensation reaction type silicone; have second area from described condensation reaction type resin on the base material side high concentration of described sealer ground, and the surface chemistry of described first area and described second area bonding described fissility composition and described adhesive ingredients are arranged.
2. surface protective film, it is the surface protective film that is provided with sealer in the one side of transparent polymer film, it is characterized in that,
The condensation reaction type silicone resin that in will generating JIS R3257:1999 and contact angle water become the solidfied material more than 100 degree is made as Resin A, the condensation reaction type resins that the contact angle with water among the generation JIS R3257:1999 become the following solidfied material of 90 degree are made as resin B, the condensation reaction type silicone resin that is included in the category of this resin B is made as resin B 1, when other condensation reaction type resins beyond the described resin B 1 that is included in the category of described resin B are made as resin B 2
Described sealer is formed by the solidfied material of the coating composition with fissility composition and adhesive ingredients; described fissility composition comprises Resin A; described adhesive ingredients comprises the resin B that contains resin B 1 with the scope below the 70 weight % more than the 15 weight %; and; non-base material side at described sealer is that face side high concentration ground exists the first area from Resin A; there is second area from resin B on the base material side high concentration of described sealer ground; and at the interface of described first area and described second area, by between Resin A and resin B 2, coming chemical ground described fissility composition of bonding and described adhesive ingredients across resin B 1.
3. surface protective film according to claim 1 is characterized in that,
With respect to described adhesive ingredients 100 weight portions, the resinoid ratio of described condensation reaction type silicone is 1 weight portion~40 weight portions.
4. according to any described surface protective film in the claim 1~3, it is characterized in that,
Another side at described transparent polymer film is provided with adhesive coating.
5. a surface protection film composition is characterized in that,
Have fissility composition and adhesive ingredients, described fissility composition comprises the condensation reaction type silicone resin that the contact angle with water that generates among the JIS R3257:1999 becomes the above solidfied material of 100 degree, and described adhesive ingredients comprises the condensation reaction type resin that the contact angle with water that generates among the JIS R3257:1999 becomes the following solidfied material of 90 degree.
6. surface protection film composition according to claim 5 is characterized in that,
Described condensation reaction type resin contains: the contact angle with water among the generation JIS R3257:1999 becomes the condensation reaction type silicone resin of the following solidfied material of 90 degree.
7. surface protection film composition according to claim 6 is characterized in that,
Containing the contact angle with water among the generation JIS R3257:1999 that 15 weight % are above and 70 weight % are following of described condensation reaction type resin becomes the condensation reaction type silicone resin of the following solidfied material of 90 degree.
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