KR20130129844A - Surface treating film, surface protection film, and precision electrical and electronic components attached with the same - Google Patents

Abstract

Provided are a surface treating film capable of preventing oligomer from contaminating products or surrounding areas by preventing oligomer from being extracted from the inside of a base film even when the present invention is used for heat treatment at high temperatures and an electrical and electronic component attached with the surface treating film. A layer of an adhesive agent (2) is laminated on one side of a base film (1) having flexibility on a surface protection film (10). A desquamation film (4) desquamated on the layer of an adhesive agent is laminated on a surface (4a). The surface is laminated on the surface protection film (10), wherein a protection layer (3) capable of preventing oligomer from the base film (1) from being extracted even after heat treatment at 160 for 60 minutes on at least on the other side of the base film (1) is formed. The protection layer (3) comprises epoxy resin, thin films of a resin composition including an amine hardner, and polyester resin having a functional group reacting an epoxy group.

Description

SURFACE TREATING FILM, SURFACE PROTECTION FILM, AND PRECISION ELECTRICAL AND ELECTRONIC COMPONENTS ATTACHED WITH THE SAME}

This invention relates to the surface protection film and surface treatment film used for the heat processing at high temperature. More specifically, the present invention is a surface treatment film capable of preventing the oligomers from depositing on the surface from the inside of the base film even when used for heat treatment at a high temperature, thereby preventing the oligomer from contaminating the surrounding working environment or the product. , Surface protection films and precision electrical and electronic components bonded thereto.

Conventionally, in the technical fields, such as a touch panel, an electronic paper, an electromagnetic shielding material, various sensors, a liquid crystal panel, organic electroluminescent, and a solar cell, it is ITO (indium tin oxide compound) transparent conduction to one surface of a base material, for example. Background Art A transparent conductive film (hereinafter sometimes referred to simply as a "conductive film") in which a film, a ZnO-based transparent conductive film, or a transparent polymer conductive film is formed is widely used for forming transparent electrodes and the like.

In addition, in the electric apparatus and electronic apparatus equipped with the control circuit which carries out an automatic control function, forming a high density wiring circuit by arrange | positioning many electronic components on a rigid printed wiring board is performed. In recent years, flexible printed wiring boards (hereinafter sometimes abbreviated as "FPC") in which electronic components are mounted at high density by a small case have been employed in mobile phones, portable PCs, and various mobile devices.

In addition, the FPC is a wiring circuit after forming a wiring circuit in a conductor foil by a chemical etching method on a resin conductor foil laminate in which a resin of dielectric such as polyimide is laminated on one surface of a conductor foil such as copper foil. It is manufactured by laminating | stacking a coverlay resin layer on the conductor foil which provided this. In the process of laminating | stacking a coverlay resin layer on the conductor foil of FPC, it laminates using an adhesive agent. In order to harden this adhesive agent, there exists a process of heat-pressing at the temperature of 150 degreeC or more. In the manufacturing process of FPC, by covering the resin layer surface of the resin conductor foil laminated body with a surface protection film, the mixing of chemicals and foreign substances for an etching, and the occurrence of a scratch are prevented, and also the handleability of a resin conductor foil laminated body is improved. I'm making it. In this FPC surface protection film, since it is excellent in chemical resistance and heat resistance, and it is comparatively cheap, the surface protection film which laminated | stacked the adhesive layer on the polyester film of a base material is generally used. In recent years, with the high integration of electronic devices, fine line and high density of wiring boards are progressing, and it is calculated | required to remove the small foreign material and defect which were not a problem conventionally. As a surface protection film, in the case of the surface protection film which laminated | stacked the adhesive layer on the polyethylene terephthalate film of a base material, when the heat processing process at high temperature passes, the oligomer contained in the polyethylene terephthalate of a base material of the surface protection film A problem arises, such as depositing from the inside of a base material to the surface, to contaminate the apparatus and components of a manufacturing process, or to contaminate the conductor thin surface used as a product.

On the other hand, in the manufacturing process of the transparent electrode for touch panels, the crystallization process of the metal oxide film which anneals the transparent conductive film in which the transparent conductive film which consists of ITO was formed, the printing process of a resist, an etching process process, the wiring circuit by silver paste It goes through many heating processes and chemical liquid processing processes, such as a formation process, the printing process of an insulating layer, and a punching process. In the manufacturing process of such a transparent electrode, the surface protection film for transparent conductive films is bonded together and used in order to prevent a contamination and damage to the surface on the opposite side to the surface in which the transparent conductive film of the transparent conductive film was formed. In the manufacturing process of a transparent electrode, since annealing process, formation of the wiring circuit by a silver paste, etc. are heat-processed at the temperature of about 150 degreeC, heat resistance is calculated | required by the protective film for transparent conductive films. Moreover, with the thinning of a display, the transparent conductive film to be used is also thinning. There is a demand for a surface protective film for transparent conductive films capable of improving the handling properties of the thinned transparent conductive film and improving workability in the manufacturing process of the transparent conductive film.

In such a situation, in view of having transparency and heat resistance and relatively inexpensive, a polyester film is generally employed as the base material of the surface protection film. In addition, as the display screen of the display panel becomes higher in quality, the demand for appearance quality for various optical films that are used members becomes more stringent, and appearance defects that have not been regarded as defects in the past have also been regarded as defects. For this reason, the external appearance fault resulting from the oligomer of polyethylene terephthalate which precipitates from the base film of a surface protection film becomes a cause of the external appearance defect of a transparent conductive film.

Accordingly, various methods have been proposed in order to prevent the oligomer from being precipitated from the inside of the base film during the heat treatment at a high temperature. For example, in patent documents 1 and 2, the polyester composition which contains 0.1-20 weight% of polyester plasticizers, and whose ethylene terephthalate cyclic trimer content is 0.5 weight% or less is proposed.

Moreover, the patent document 3 is proposed the coating film which apply | coated the compound which has quaternary ammonium base on the surface of a polyester film, and the coating liquid containing polyvinyl alcohol, and patent document 4 has a grade 4 on the surface of a polyester film. The polyester film for protective films which have an antistatic layer which consists of ammonium base etc. are proposed.

Moreover, after forming the primer layer which consists of a silane coupling agent etc. on the polyester films in patent documents 5 and 6, the release film which forms a release layer is proposed. Polyester oligomer prevention function is provided by the primer layer.

Japanese Unexamined Patent Publication No. 10-95905 Japanese Unexamined Patent Publication No. 10-95906 Japanese Laid-Open Patent Publication 2003-237005 Japanese Unexamined Patent Publication No. 2007-023174 Japanese Laid-Open Patent Publication 2001-246699 Japanese Laid-Open Patent Publication No. 2008-006750

Thus, the method of preventing an oligomer from depositing from a base film at the time of heat processing at high temperature is known.

However, in the countermeasure which prevents precipitation of the oligomer of patent document 1, 2, since the polyester film with few oligomers in a base film is manufactured, it is necessary to change from resin to be used, and it takes a lot of time and effort. It is difficult to manufacture with a small lot.

Moreover, all the protective films of patent documents 3 and 4 process at the time of film forming and extending | stretching of a polyester film, and since it requires a large manufacturing facility, it is difficult to manufacture by a small lot. Moreover, it is technically difficult to apply | coat an aqueous coating liquid uniformly about film forming and the stretched polyester film.

In addition, in the release films of patent documents 5 and 6, since a silane coupling agent is a low molecule, only coating in a thin film can be performed. For this reason, there exists a limit to the effect which prevents precipitation of a polyester oligomer, and the effect which prevents precipitation of an oligomer is inadequate when the heating temperature is high or the conditions exposed to high temperature over a long time.

As mentioned above, in the manufacturing process of a flexible printed wiring board, the transparent electrode for touch panels, etc., about the surface protection film used for the heat processing process at high temperature, there is no precipitation of the oligomer from a base film even after a heating process. Or less is required. However, in the prior art, sufficient solutions have not been made.

This invention is made | formed in view of the said situation, Even if it uses for the heat processing at high temperature, it is prevented that an oligomer precipitates on the surface from the inside of a base film, and suppressing that an oligomer contaminates an surrounding working environment or a product. It is an object of the present invention to provide a surface treatment film, a surface protection film, and a precision electric / electronic component bonded thereto.

In order to solve the said subject, this invention forms the protective layer which can prevent precipitation of the oligomer resulting from a base film in the surface protection film and surface treatment film used at the process of heat-processing at high temperature. It is technical idea.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, in this invention, an adhesive layer is laminated | stacked on one surface of a flexible base film, and the peeling film peeled on the surface of the said adhesive layer is laminated | stacked through the said peeled surface. The surface protection film which provides the protective layer which can prevent precipitation of the oligomer resulting from the said base film even after heat-processing for temperature 160 degreeC * 60 minutes on the at least other surface of the said base film.

Moreover, this invention is the protective layer which can prevent precipitation of the oligomer which originates in the said base film, even after heat-processing for temperature 160 degreeC x 60 minutes in the at least one surface of the flexible base film. Provide a surface treatment film.

Moreover, it is preferable that the said protective layer consists of an epoxy resin, the polyester resin which has a functional group which reacts with an epoxy group, and the thin film of the resin composition containing an amine-type hardening | curing agent.

Moreover, it is preferable that the said base film is the polyester film extended | stretched biaxially.

It is preferable that the said adhesive is an acrylic adhesive.

Moreover, this invention is a precision electrical / electronic component by which the said surface protection film is bonded together, The precision electrical / electronic component selected from the precision electrical / electronic component group which consists of a flexible printed wiring board, a rigid printed wiring board, a transparent conductive film, etc. Provide electronic components.

The surface treatment film and surface protection film of this invention prevent an oligomer from depositing on the surface from the inside of the base film which comprises a surface treatment film and a surface protection film even if it is used for the heat processing at high temperature, and the said oligomer surrounds the surroundings. Contamination of the working environment and products can be suppressed.

For this reason, the precision electrical / electronic component in which the surface protection film of this invention was bonded is protected from the mixing of a chemical | medical agent and a foreign material, and a mark, and the effect which can aim at the improvement of workability and an improvement of a production efficiency is exhibited.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example of the surface protection film which concerns on this invention.
It is a schematic sectional drawing which shows the example of the precision electrical / electronic component in which the surface protection film of this invention was bonded.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on embodiment.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example of the surface protection film which concerns on this invention. In this surface protection film 10, the adhesive layer 2 is formed in one surface of the transparent base film 1. As shown in FIG. On the surface of the pressure-sensitive adhesive layer 2, a peeled release film 4 (or a peeled film 4 that is not peeled off. Also referred to as a cover film) for protecting the adhesive face is laminated. The protective layer 3 for suppressing precipitation of an oligomer is laminated | stacked on the surface on the opposite side to the surface where the adhesive layer 2 of the base film 1 was laminated | stacked.

As the base film 1 used for the surface protection film of this invention, the resin film which has transparency is used. Thereby, an external appearance test can be performed, bonding a surface protection film together to precision electrical / electronic components, such as a flexible printed wiring board which is a to-be-adhered body, a rigid printed wiring board, and a transparent conductive film. As a result, the work which peels a protective film from a to-be-adhered body, and the operation which bonds a surface protection film again can be skipped in order to perform an external appearance inspection, and can improve work efficiency.

Moreover, as a resin film used for the base film 1 of the surface protection film of this invention, polyester films, such as polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, polybutylene terephthalate, are used preferably. . Although the base film 1 does not have a restriction | limiting in particular, such as a non-stretched resin film, the uniaxial or biaxially stretched resin film, It is preferable that the heat shrinkage rate in MD direction and TD direction of a resin film is 0.5% or less.

In addition, the thickness of the base film 1 used for the surface protection film of this invention is not specifically limited. The thickness of the base film 1 is selected in consideration of the thickness of a precision electrical / electronic component which is an adherend, a manufacturing process, and the like. As thickness of the base film 1, the thickness of about 25-250 micrometers is preferable. As for the thickness of the base film 1 used, when the surface protection film used for the protection of the thin-filmed functional film (for example, whose total thickness is 100 micrometers or less), the thickness of about 50 micrometers-188 micrometers is more preferable, The thickness of about 75 micrometers-188 micrometers is more preferable.

In addition, the base film 1 used for the surface protection film of this invention may surface-treat an annealing process, a plasma process, a corona discharge process, an anchor coat, etc. as needed.

As for the adhesive layer 2 used for the surface protection film of this invention, the adhesive with a small change of adhesive force is good before and after the heating process at high temperature, and an acrylic adhesive is used preferably. As a composition of an acrylic adhesive, the adhesive composition which added the hardening | curing agent and a tackifier to the main component which consists of a (meth) acrylic-type polymer can be used as needed.

Moreover, as a (meth) acrylic-type polymer, Main monomers, such as n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, and isononyl acrylate, acrylonitrile, vinyl acetate, methyl methacrylate, Polymers copolymerized with functional monomers such as comonomers such as ethyl acrylate, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxybutyl acrylate, glycidyl methacrylate, and N-methylol methacrylamide Generally can be used.

Moreover, an isocyanate compound, an epoxy compound, a melamine compound, a metal chelate compound, etc. are mentioned as a hardening | curing agent.

Examples of the tackifier include rosin, coumarone indene, terpene, petroleum, phenol and the like.

You may mix antistatic agent with the adhesive layer 2 used for the surface protection film of this invention as needed. As an antistatic agent, the thing with favorable dispersion or compatibility with respect to a (meth) acrylic-type polymer is preferable. Examples of the antistatic agent that can be used in the present invention include surfactants, ionic liquids, alkali metal salts, metal oxides, metal fine particles, conductive polymers, carbon, carbon nanotubes, and the like. In terms of affinity and the like, a surfactant system, an ionic liquid, an alkali metal salt, and the like are preferable. The amount of the antistatic agent added to the pressure-sensitive adhesive varies depending on the type of the antistatic agent and the degree of compatibility with the base polymer, but is appropriately selected in consideration of the peeling electrification voltage, adherend contamination, and adhesive properties when peeling the surface protective film. do.

Although the thickness of the adhesive layer 2 of the surface protection film which concerns on this invention is not specifically limited, For example, it is preferable to set it as thickness of about 3-40 micrometers, and to set it as thickness of about 5-30 micrometers more. desirable. If the thickness of the pressure-sensitive adhesive layer (2) is thicker than 40㎛, manufacturing cost increases, so the price competitiveness is low.

Moreover, the adhesive layer 2 of the surface protection film of this invention has the adhesive force of the adhesiveness of the hardness whose peeling strength with respect to the surface of a to-be-adhered body is about 30-300 mN / 25 mm (0.03-0.3 N / 25 mm). It is preferable that it is an adhesive layer.

The method of forming the adhesive layer 2 on the surface of the base film 1 of the surface protection film which concerns on this invention can employ | adopt a well-known method. Specifically, well-known coating methods, such as a reverse coat, a comma coat, a gravure coat, a slot die coat, a Meyer bar coat, an air knife coat, can be used.

The material of the peeling film 4 used for the surface protection film which concerns on this invention is not specifically limited. As a specific material of the release film 4, polyolefin films, such as a polyethylene film, a polypropylene film, and a polymethyl pentene film, resin films, such as a polyester film and a polyimide film, are used individually, for example, As a base material, the peeling film which carried out the peeling process using the silicone type, the fluorine type, or the organic type peeling agent can be used as a base material. The peeling process peeled film 4 is laminated | stacked on the surface of the adhesive layer 2 through the peeling process 4a.

When the resin film which is not peeled off is used for the peeling film 4 by itself, it is laminated | stacked on the surface of the adhesive layer 2 through the one surface 4a of the peeling film 4. The peeling strength of the surface 4a of the peeling film 4 with respect to the adhesive surface of the adhesive layer 2 does not have a possibility of peeling when carrying out storage or transportation of a surface protection film, and an adhesive when bonding a surface protection film The extent to which the layer 2 is easily peeled off so that the adhesive does not adhere to the surface 4a and does not damage the surface (adhesive surface) of the adhesive layer 2 is preferable.

In the surface protection film which concerns on this invention, the method of laminating | stacking in order of the adhesive layer 2 and the peeling film 4 on the surface of the base film 1 may be performed by a well-known method, It does not specifically limit. Specifically, after applying and drying an adhesive composition to the base film 1, and forming the adhesive layer 2, to the method of bonding the release film 4 on the adhesive layer 2, and the release film 4, After apply | coating and drying an adhesive composition and forming the adhesive layer 2, you may employ | adopt any method, such as a method of bonding the base film 1 together.

In the surface protection film which concerns on this invention, the protective layer 3 for suppressing precipitation of an oligomer from the base film 1 is formed in the surface on the opposite side to the surface in which the adhesive layer 2 of the base film 1 was formed, It is characterized by that. As the protective layer 3 for suppressing precipitation of an oligomer, the thin film layer which consists of an epoxy resin, the polyester resin which has a functional group which reacts with an epoxy group, and a resin composition containing an amine-type hardener is preferable.

Moreover, it does not specifically limit as an epoxy resin used for the protective layer 3 of the surface protection film which concerns on this invention. Various epoxy resins, such as a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a bisphenol B-type epoxy resin, an acrylic epoxy resin, a novolak-type epoxy resin, are mentioned, These can be used individually or in 2 or more types. Among these, it is preferable to use the bisphenol-A epoxy resin which has two epoxy groups in 1 molecule from the point which is excellent in the adhesiveness and stability of the protective film obtained.

As a commercially available bisphenol-A epoxy resin which is generally available, for example, YD-011, YD-012, YD-013, YD-901, YD-8125 (Toto Kasei Co., Ltd. make, brand name: Epoch) Sat), jER828, jER834, jER1001, jER1004, jER1007 (manufactured by Mitsubishi Chemical Corporation), epiclone 850, epiclone 1050, epiclone 3050, epiclone 4050, epiclone 7050, HM-091 (manufactured by DIC Corporation), NER-1202, NER-1302 (manufactured by Nippon Gunpowder Co., Ltd.), DER331, DER661, DER664, DER667 (manufactured by Dow Chemical Nihon Corporation), Epicoat 834, Epicoat 1001, Epicoat 1003, Epicoat 1004 (Yuka) Shell epoxy).

Moreover, as polyester resin which has a functional group reacting with the epoxy group used for the protective layer 3 of the surface protection film which concerns on this invention, It is a polyester resin obtained from polyhydric carboxylic acid or its derivative (s), and a polyhydric alcohol, and is 1 molecule. The carboxyl group-containing polyester resin which has at least 2 carboxyl group is mentioned in this.

As a specific example of polyhydric carboxylic acid or its derivative (s), Aromatic dicarboxylic acids, such as isophthalic acid, terephthalic acid, phthalic anhydride, 2, 6- naphthalenedicarboxylic acid, 2, 7- naphthalenedicarboxylic acid, and these Aromatic dicarboxylic acid esters such as anhydride, isophthalic acid dimethyl ester and terephthalic acid dimethyl ester, aliphatic dicarboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, and hexahydrophthalic anhydride These may be mentioned, You may combine these individually or 2 types or more.

Moreover, as a specific example of polyhydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol, trimethylol propane, propylene glycol, dipropylene glycol, 1, 6- hexanediol, neopentyl glycol, hydrogenated bisphenol A, 1, 4 -Butanediol, 1,4-cyclohexanediol, 2,2,4-trimethylpentane-1,3-diol, polyethyleneglycol, etc. are mentioned, These can be used individually or in 2 or more types.

The use ratio of the said carboxyl group-containing polyester resin and an epoxy resin in the resin composition for protective layers 3 is 0.5-1.5, Preferably 0.8-1.2 is the number of epoxy groups per carboxyl group of a carboxyl group-containing polyester resin. The range which becomes is very preferable.

In addition, a carboxyl group-containing polyester resin can be manufactured by polycondensation-reacting the acid component which has polyhydric carboxylic acid as a main component, and the alcohol component which has polyhydric alcohol as a main component by a well-known method as a raw material, for example. Instead of polyhydric carboxylic acid, polyhydric carboxylic acid esters may be used to prepare by polymerization reaction involving transesterification with polyhydric alcohol.

As a commercially available carboxyl group-containing polyester resin generally available, Z-561, Z-730, Z-880, RZ-142 (manufactured by Koo Chemical Co., Ltd., product name: plastic coat), A-110, A-210, A-620 (manufactured by Takamatsu Oil Co., Ltd., product name: PES resin), MD-1200, MD-1220, MD-1250, MD-1335, MD-1400, MD-1480, MD-1500 (Toyo Spinning Co., Ltd. make, brand name: Vironal), a krill coat 341, a krill coat 7630, a krill coat 7624 (made by Daicel UCB Co., Ltd.), etc. are mentioned.

It is preferable to use an amine hardening | curing agent for the surface protection film of this invention as a hardening | curing agent for hardening | curing the epoxy resin contained in the protective layer 3. As an amine-type hardening | curing agent, methyl imidazole, methyl imidazoline, dodecyl imidazole, dodecyl imidazoline, heptadecilimidazole, heptadecilimidazoline, phenyl imidazole, phenyl Imidazoles such as imidazolines and derivatives thereof, aliphatic polyamines such as polyetheramine, ethylenediamine, diethylenetriamine, trimethylenediamine, tetramethylenediamine, triethylenetetramine, metaxylylenediamine, and hexamethylenediamine; The derivatives thereof, mensendiamine, 1,2-diaminocyclohexane, isophoronediamine, piperazine, N-aminoethylpiperazine, 1,3-bis (aminomethyl) cyclohexane, metaxylenediamine, bis (4- Alicyclic polyamines and derivatives thereof such as amino-3-methylcyclohexyl) methane and polycyclohexyl polyamine, aromatic polyamines and derivatives thereof such as metaphenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone, melamine and benzo Heterocyclic amines and derivatives thereof such as guanamine, organic acid hydrazide compounds and derivatives thereof such as dicyandiamide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid dihydrazide, melamine resins, And amino resins such as benzoguanamine resin, melamine-benzoguanamine cocondensation resin, urea resin, melamine-urea cocondensation resin and aniline resin. These can be used individually or in 2 or more types.

Moreover, in addition to an amine hardening | curing agent, a diluent, a hardening accelerator, a coupling agent, a modifier, a filler, etc. can be added to the protective layer 3 of the surface protection film of this invention as needed. In this invention, since the viscosity of the resin composition for protective layer formation is adjusted to be suitable for an application | coating operation, it is possible to use a well-known epoxy resin diluent as a diluent, For example, the reactive diluent which has one epoxy group per molecule. , Aromatic diluents, solvents, and the like.

In addition, the thickness of the protective layer 3 of the surface protection film which concerns on this invention is although it does not specifically limit, For example, thickness of about 0.05-10 micrometers is preferable, and thickness of about 0.1-1 micrometer is more preferable. Do. In addition, what is necessary is just to implement the method of forming the protective layer 3 of the surface protection film which concerns on this invention by a well-known method. Specifically, well-known coating methods, such as a reverse coat, a comma coat, a gravure coat, a slot die coat, a Meyer bar coat, an air knife coat, can be employ | adopted. The resin composition for forming the protective layer 3 which suppresses precipitation of an oligomer coated on the base film 1 can be hardened by applying energy by heating, ultraviolet irradiation, infrared irradiation, electron beam irradiation, or the like. As needed, in order to promote the hardening reaction of the protective layer 3 which suppresses precipitation of an oligomer more, you may perform curing to keep for a certain period of time, maintaining the temperature about 40-60 degreeC. Moreover, in order to improve the adhesiveness of the protective layer 3 which suppresses precipitation of an oligomer, and the base film 1, you may perform preprocessing, such as a corona treatment, a plasma process, and an anchor coat, beforehand.

It is a schematic sectional drawing which shows the example of the precision electrical / electronic component in which the surface protection film of this invention was bonded. After peeling the peeling film 4 from the said surface protection film 10, it bonds to the surface of the precision electrical / electronic component 7 through the adhesive layer 2. As a specific example of the precision electrical and electronic components 7, a flexible printed wiring board, a rigid printed wiring board, a transparent conductive film, a touch panel, an electronic paper, an electromagnetic shielding material, various sensors, a liquid crystal panel, an organic EL, a solar cell, etc. Can be mentioned.

Even if the surface protection film 10 of this invention carries out the heating process at high temperature, an oligomer rarely precipitates from the inside of the base film 1, and contaminates a working environment, a flexible printed wiring board, a conductive film, etc. which are products. This can be suppressed. For this reason, since the precision electrical and electronic component 20 to which the surface protection film 5 of this invention was bonded is protected from the mixing of chemicals and a foreign material, and a mark, it can improve workability and production efficiency.

Moreover, even after the surface treatment film 6 of this invention heat-processes 160 degreeC * 60 minutes (s) at least one surface of the flexible base film 1, of the oligomer which originates in the base film 1 By forming the protective layer 3 which can prevent precipitation, the surface of the base film 1 is a film processed. The surface treatment film 6 can be used as a support body etc. of the adhesive layer 2 in the surface protection film 5.

Example

Next, based on an Example, this invention is further demonstrated.

(Production of the surface protective film of Example 1)

On one side of a biaxially stretched polyethylene terephthalate film having a thickness of 50 µm, an average molecular weight of 7000 consisting of neopentylglycol and ethylene glycol as an acid component and neopentyl glycol and ethylene glycol as an acid component, 70 parts by weight of an acid value of 25 mgKOH, 5 parts by weight of bisphenol A epoxy resin having an average molecular weight of 1400, a resin composition composed of 25 parts by weight of an amino resin obtained by mixing a melamine resin and a benzoguanamine resin in a ratio of 3: 7 so that the thickness after drying is 0.1 μm, It coated using the Meyer bar method and laminated | stacked the protective layer. Then, in a 140 degreeC hot air circulation type dryer, it heated for 1 minute and dried the protective layer, and formed the thin film of the protective layer on one side of the base film.

Thereafter, HDI-based curing agent (Nippon Polyurethane) was used for 100 parts by weight of the acrylic pressure-sensitive adhesive composition having a solid content of 40% by copolymerizing butyl acrylate, 2-ethylhexyl acrylate, acrylic acid, and 2-hydroxyethyl acrylate. 2.4 weight part of industrially produced coronate HX) was added, and the mixed adhesive composition was obtained. After apply | coating the obtained adhesive composition on the opposite side to the surface in which the thin film of the protective layer of the base film was formed so that thickness after drying might be set to 5 micrometers, it dried for 2 minutes in 100 degreeC hot-air circulation type oven, and forms an adhesive layer. It was. Then, the 40-micrometer-thick biaxially stretched polypropylene film was bonded together on the surface of an adhesive layer as a peeling film, and the surface protection film of Example 1 was obtained.

(Production of the surface protection film of the comparative example 1)

The surface protection film of Comparative Example 1 was obtained in the same manner as in Example 1 except that the protective layer using the coating material of the resin composition composed of an epoxy resin, a polyester resin, and an amino resin curing agent was not formed.

Hereinafter, it shows about the method and the result of an evaluation test.

(Initial Adhesion of Surface Protective Film)

After cut | disconnecting the surface dimension film of obtained Example 1 and the comparative example 1 to 25 mm, the peeling film is peeled off, and it is an adhesive to the polyimide film (made by Dupont, brand name: Kapton 100H) whose thickness is 25 micrometers. It bonded together through the layer and set it as the laminated body. Then, the laminated body was stored for 1 hour in 23 degreeC x 50% RH environment. Then, the intensity | strength at the time of peeling a surface protection film in 180 degree directions at the peeling speed of 300 mm / min was measured using the tensile tester, and this was made into initial stage adhesive force (mN / 25mm).

<Adhesive force after heating of the surface protection film>

After cut | disconnecting the surface dimension film of obtained Example 1 and the comparative example 1 to 25 mm, the peeling film is peeled off, and it is an adhesive to the polyimide film (made by Dupont, brand name: Kapton 100H) whose thickness is 25 micrometers. It bonded together through the layer and set it as the laminated body. Then, the laminated body was stored for 1 hour in 150 degreeC environment. Thereafter, the laminate was left to stand for 1 hour in an environment of 23 ° C. × 50% RH, and the strength when the surface protective film was peeled off in the direction of 180 ° at a peel rate of 300 mm / min using a tensile tester was measured. This was made into adhesive force (mN / 25mm) after heating.

(Observation method of oligomer precipitation)

After bonding the surface protection films of Example 1 and Comparative Example 1 to the polyimide film (the DuPont company make, product name: Kapton 100H) which is 25 micrometers in thickness, it cuts to the dimension of width 100mm x length 100mm, and evaluates A sample was obtained. The obtained evaluation sample was heat-processed for 160 degreeC x 60 minutes or 200 degreeC x 30 minutes. Then, after cooling the sample for evaluation to room temperature, the surface of the protective layer formed in the surface protection film was observed with the optical microscope (20 times magnification), and the presence or absence of precipitation of the oligomer was observed.

Almost no thing ((O)) and many thing (X) which made little oligomer precipitation were made into (xx).

Table 1 shows the measurement results for Example 1 and Comparative Example 1.

The following is understood from the measurement result shown in Table 1. In the protective film according to the present invention of Example 1, the oligomer is less likely to precipitate from the inside of the base film even after the heating process is performed at a temperature of 160 ° C. for 60 minutes or 200 ° C. for 30 minutes, contaminating the working environment and the product. There is no case.

On the other hand, in the surface protection film of the comparative example 1 in which the protective layer is not formed, after the heating process for temperature 160 degreeC x 60 minutes, the oligomer precipitated in large quantities from the inside of the base film to the surface. After going through a heating step at a temperature of 200 ° C. for 30 minutes, a great number of oligomers were deposited.

Although the surface protection film of this invention is used for the heat processing at high temperature, it can prevent that an oligomer precipitates from the inside of the base film which comprises a surface protection film, and the oligomer contaminates the surrounding working environment or a product. It can be suppressed.

Thereby, the workability and production efficiency of the manufacturing process of the transparent electrode for touch panels, for example can be improved significantly. Moreover, the surface protection film of this invention is a precision printed circuit board, a rigid printed wiring board, a transparent conductive film, a touch panel, electronic paper, electromagnetic shielding materials, various sensors, liquid crystal panels, organic electroluminescent, solar cells, etc. It can be used widely as a surface protection film for manufacture and processing of components.

One… Base film, 2... Pressure-sensitive adhesive layer; Protective layer, 4... Release film, 5... Surface protection film which peeled release film, 6.. Surface treatment film, 7... Precision electrical and electronic components, 10... Surface protection film, 20... Precision electric and electronic parts which bonded surface protection film.

Claims (10)

An adhesive layer is laminated | stacked on one surface of the base film which has flexibility, and the peeling film which peeled on the surface of the said adhesive layer is laminated | stacked through the said peeled surface, and it is at least another surface of the said base film The surface protection film in which the protective layer which can prevent precipitation of the oligomer resulting from the said base film is formed even after heat processing for temperature 160 degreeC * 60 minutes. The method of claim 1,
The surface protection film which consists of a thin film of the resin composition which the said protective layer has an epoxy resin, the polyester resin which has a functional group which reacts with an epoxy group, and an amine-type hardening | curing agent. 3. The method according to claim 1 or 2,
The surface protection film whose said base film is a biaxially stretched polyester film. 3. The method according to claim 1 or 2,
The surface protection film whose said adhesive is an acrylic adhesive. The precision electrical / electronic component formed by bonding the surface protection film of claim 1 or 2, wherein the precision electrical / electronic component selected from the group of precision electrical / electronic components comprising a flexible printed wiring board, a rigid printed wiring board, and a transparent conductive film. Electronic parts. The surface treatment film in which the protective layer which can prevent precipitation of the oligomer resulting from the said base film is formed even after heat-processing for temperature 160 degreeC * 60 minutes on the at least one surface of a flexible base film. The method according to claim 6,
The surface treatment film which the said protective layer consists of a thin film of the resin composition containing an epoxy resin, the polyester resin which has a functional group which reacts with an epoxy group, and an amine-type hardening | curing agent. The method according to claim 6 or 7,
The surface treatment film whose said base film is a biaxially stretched polyester film. The method according to claim 6 or 7,
The surface treatment film whose said adhesive is an acrylic adhesive. The method of claim 8,
The surface treatment film whose said adhesive is an acrylic adhesive.

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