KR100816694B1 - Board Masking Tape - Google Patents

Abstract

An object of the present invention is to increase the undesired thickness of a thin film (coating film) due to undesired enlargement of the coating shape of the thin film (coating film) around the tape when the coating liquid made of a flowable material is applied onto a substrate to form a thin film. It is to provide a masking tape that can prevent the occurrence of.

The masking tape 10 for a board | substrate of this invention is equipped with the base material 1 and the adhesion layer 3 formed in one surface of the base material 1, and the other surface A of the base material 1 The contact angle of water in E is less than 65 °, and the contact angle of water in side (B) of the adhesive layer 3 is less than 100 °. By the tape 10, at the time of forming a thin film (coating film) of a fluid material such as a water dispersible conductive material, formation of a meniscus on the side of the adhesive layer 3 and the other surface of the substrate 1 are formed. Falling of the fluid material from (A) is suppressed, and it becomes possible to form a thin film with a uniform film thickness.

Description

Board masking tape {MASKING TAPE FOR SUBSTRATE}

1: is a perspective view which shows one Embodiment of the masking tape for board | substrates of this invention.

FIG. 2: is sectional drawing which shows one Embodiment of the masking tape for board | substrates of this invention, FIG. 2 (a) is sectional drawing which shows one Embodiment of the masking tape for board | substrates of this invention, and FIG. 2 (b) is this invention It is sectional drawing which concerns on other embodiment of the masking tape for board | substrates.

Fig. 3 is a view for explaining the wettability test of the masking tape side. Fig. 3 (a) is a view in which a masking tape is applied, a water dispersible conductive material is dropped, and is left for 24 hours, and Fig. 3 (b) is 24. It is a figure of the state which peeled masking tape after leaving to stand.

* Description of the symbols for the main parts of the drawings *

1: description

3: adhesion layer

5: separator

10: masking tape for substrate

20: masking tape for the substrate

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a masking tape for a substrate, and more particularly, to an organic EL material for various substrates such as an organic EL substrate, a liquid crystal substrate, an organic thin film solar cell substrate, a plasma display substrate, a semiconductor wafer, and an optical disk substrate. The present invention relates to a masking tape for a substrate used when a fluid material such as a conductive material or a photoresist is applied to form a thin film.

The organic electroluminescent display (OELD) has the best visibility as a next-generation display in view of excellent visibility due to high luminance, wide viewing angle, high-speed response, etc. due to self-luminous, thin, light weight, low power consumption, and low cost. have. The organic ELD generally has a structure in which an anode (transparent electrode), an HTL (hole transporting layer), an EML (light emitting layer), an ETL (electron transporting layer), and a cathode are sequentially stacked on a glass substrate. A forming technique is applied, and the inkjet method is known as this thin film forming technique, for example.

The inkjet method is a method of freely discharging a coating liquid containing light emitting polymers (R, G, B) from a nozzle by ON / OFF, and applying the coating liquid separately for each pixel on a substrate. There is a problem that it is easy to occur, there is a limitation in the solid component ratio and viscosity of the coating liquid that can be used, and the droplets themselves may be broken in the middle. In addition, clogging due to drying of the tip of the nozzle is likely to occur, and there is a problem in maintainability.

Therefore, in recent years, the nozzle coating method which forms a thin film by discharging a coating liquid continuously from a nozzle attracts attention. In the nozzle coating method, the coating liquid filled in a bottle is sucked up by a section pump, filtered, and then sent to a discharge nozzle and continuously discharged to a substrate while forming a liquid column from the nozzle. There is no problem, and there is an advantage that the coating liquid can always be discharged at almost the same flow rate (Japanese Patent Laid-Open No. 2004-89771).

However, in the method of apply | coating a coating liquid to a board | substrate continuously with a nozzle, since the discharge control responsiveness of a coating liquid is not high, it is difficult to control on-off of discharge of a coating liquid. Therefore, since it is difficult to control the discharge of the coating liquid on and off while the nozzle is being scanned on the substrate, the coating liquid cannot be applied by selecting only the region requiring the coating during scanning. Therefore, when applying nozzle application | coating, after apply | coating a coating liquid also to the area | region in which application | coating on a board | substrate is unnecessary, you should remove the coating liquid apply | coated to the area | region where application | coating is unnecessary. For example, the four corners of the four corners of the substrate become an application-free area. In the case of applying the nozzle, as a method of removing the coating liquid from the application unnecessary area of the substrate, there is a method of masking the application unnecessary area with a masking tape or a masking member. In addition, in the case of producing a plurality of display panels from a single substrate by the nozzle coating method, since the coating liquid is also discharged between the adjacent display panel and the display panel, application is performed by separating the adjacent display panels. Can not.

The present inventors discharged a fluid material to a glass substrate by the nozzle coating method, adhere | attached the conventionally well-known masking tape to the application | coating unnecessary area | region, and implemented the measure which prevents coating liquid from apply | coating between adjacent display panels, respectively. There was a problem that the thickness of the thin film by the coating liquid formed in the display panel (area in which the thin film should be formed) was thickened by an undesired enlargement of the coated shape at the side (near the side) of the masking tape. If an unwanted increase in the thickness of the thin film occurs due to an undesired enlargement of the coating shape of the flowable material, then, for example, when the material for the cathode is deposited on both ends of the display panel (the area where the thin film should be formed). There is a concern that the cathode may be disconnected at a portion where the coating shape of the thin film by the flowable material is enlarged or the moisture or oxygen cannot be blocked by the deposited cathode.

In view of the above circumstances, the problem to be solved by the present invention is to provide a thin film (coating film) around a tape when a thin film is formed by masking a coating-free area on a substrate with a masking tape and applying a coating liquid made of a flowable material. It is to provide a masking tape which can prevent the increase in thickness that does not occur.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, when investigating the cause of the increase of the unwanted thickness which arises in the thin film (coating film) which consists of the flowable material around a tape, when a conventionally well-known masking tape is used, the nozzle coating method When the fluid material was discharged to form a thin film, it was found that the following phenomenon occurred.

[1] The flowable material attached to the side of the masking tape forms a meniscus.

[2] The flowable material applied to the back side of the masking tape falls off on the thin film forming surface of the masking tape side.

Therefore, based on this knowledge, the present inventors have conducted research from the viewpoint of improving the wettability of the masking tape and the thin film forming material (fluid material), and the tape backing (non-adhesive layer of the substrate) and the tape side ( When the contact angle of water in the side of an adhesion layer is respectively a specific range, said [1] is suppressed and said [2] is eliminated, and the desired in a thin film (coating film) by the fluid material around a tape It has been found that the increase in the thickness can be suppressed, and the present invention has been completed.

That is, the present invention,

(1) A masking tape for a substrate having an adhesive layer on one surface of a substrate,

The contact angle of water in the other side of a base material is less than 65 degrees,

The contact angle of the water in the side of an adhesion layer is less than 100 degrees,

Substrate masking tape,

(2) the masking tape as described in said (1) which has a separator in the to-be-adhered surface of an adhesion layer,

(3) the masking tape as described in said (1) or (2) in which a base material consists of a polyester film,

(4) The masking tape in any one of said (1)-(3) which has a surface treatment layer on the other surface of a base material,

(5) The masking tape in any one of said (1)-(4) which has a surface treatment layer in the side surface of an adhesion layer,

(6) the masking tape as described in said (5) whose surface treatment layer apply | coated the photocatalyst,

(7) The masking tape in any one of said (1)-(6) whose board | substrate is a glass substrate,

(8) The masking tape in any one of said (1)-(7) whose board | substrate is an organic EL board | substrate, and

(9) It relates to the masking tape in any one of said (1)-(8) used at the time of thin film formation by the apply | coating method which apply | coats a fluid material from a nozzle toward a board | substrate.

In the present invention, "fluid material" means a material in the form of a liquid, semi-liquid, paste, melt, solution, dispersion or suspension, and means a material capable of forming a thin film on a substrate by continuous application by a nozzle. do.

Since the masking tape for substrates of this invention shows specific wettability that the contact angle of the back surface (non-adhesive layer non-formation surface of a base material) and the water side of an adhesion layer become a specific range, respectively, this is a coating unnecessary area | region (thin film formation on a board | substrate). By adhering to an area that does not need to be applied) and applying a flowable material to form a thin film, the height of the meniscus of the flowable material formed on the side (near the side) of the tape can be reduced, Dropping of the flowable material to the tape side is suppressed, and it becomes possible to stably form a thin film on the substrate (non-mask area) without causing an undesirable increase in thickness. Therefore, for example, the masking tape for a board | substrate of this invention is adhere | attached on the board | substrate for organic EL, and the area | region (display panel area | region) which should form a some thin film on the board | substrate is partitioned, and each function is carried out by the nozzle coating method. In order to form a thin film that becomes a layer in sequence and to produce a plurality of display panels (organic ELDs) from one substrate, a poor electrical conductivity due to disconnection of the cathode, a poor blocking of moisture or oxygen from the outside of the negative electrode, and the like. Can be surely prevented from occurring, and as a result, the production efficiency can be increased and the production cost can be greatly reduced.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on the preferable embodiment. In addition, in description of drawing, the same code | symbol is attached | subjected to the same element, and the overlapping description is abbreviate | omitted. In addition, for the convenience of illustration, the dimension ratio of drawing does not necessarily correspond with what is demonstrated.

(1st embodiment)

FIG. 1: is a perspective view of the masking tape for board | substrates which concerns on 1st Embodiment, and FIG. 2 (a) is sectional drawing cut along the line I-I of the masking tape for board | substrates which concerns on 1st Embodiment.

As the masking tape for board | substrates of this invention is shown to the masking tape 10 for board | substrates which concerns on the said 1st Embodiment, the adhesion layer 3 formed in the base material 1 and one surface of this base material 1 It is to be provided. The adhesive layer 3 itself has adhesiveness, and is comprised by the adhesive mentioned later. And the contact angle of the water in the other surface A of the base material 1, ie, the back surface of the masking tape 10, is less than 65 degrees, and the contact angle of the water in the side surface B of the adhesion layer is less than 100 degrees. It is characterized by.

Hereinafter, although each component of the masking tape for board | substrates is demonstrated in detail, a masking tape for board | substrates is simply called a masking tape.

(materials)

As the base material 1, as long as the contact angle of water in the other surface of a base material becomes less than 65 degrees (preferably less than 60 degrees, more preferably less than 50 degrees), it can be used without a restriction | limiting in particular. If the contact angle is 65 ° or more, when the thin film is formed, the wettability on the back side of the masking tape becomes insufficient, and the flowable material easily falls off from the back side of the masking tape. It becomes the cause of the increase of the thickness. It also causes contamination such as particles, splatters, and contamination.

Moreover, although the minimum of the contact angle of the water in the other surface of a base material is not specifically limited, 5 degrees or more are preferable and 10 degrees or more are more preferable.

In the present specification, "water contact angle" refers to a contact angle meter at 23 ° C x 50% RH within 20 seconds after attaching 3 µg of distilled water to the test surface with a glass syringe equipped with a stainless steel needle having an internal diameter of 0.4 mm. It means what is measured by the (theta) / 2 method using (brand name: CA-X type | mold, Kyowa Interface Science Co., Ltd. product). In the present invention, as described above, when the contact angle of water is measured, a base material of less than 65 ° is selected and used.

As a base material, a plastic film is used preferably, for example, Polyolefin type films, such as polyethylene and a polypropylene, specifically; Polyester-based films such as polyethylene terephthalate and polybutylene terephthalate; Polyamide film, such as nylon, a triacetyl cellulose film, a polyimide film, etc. are mentioned. Especially, a polyester film is preferable from a viewpoint of solvent resistance, water resistance, etc. In particular, the polyester film easily obtains that the contact angle of water is in the above range. Moreover, from a heat resistant viewpoint, a polyimide film is preferable. That is, when a polyimide film is used for a base material, it is preferable because the board | substrate can be heat-treated (baked) at the temperature of about 250 degreeC, for example, with a masking tape adhere | attached to a board | substrate, for example. Moreover, any of an unstretched film and an extending | stretching (uniaxial stretching or biaxial stretching) film may be sufficient as these plastic films. In addition, these plastic films can be used without any special surface treatment, as long as the contact angle of water on the surface of the film is less than 65 ° depending on the properties of the material (plastic), but otherwise, the contact angle of water on the surface is 65 °. Surface treatment which hydrophilizes the surface of the film used as the other surface of a base material is performed so that it may become less than (surface treatment layer is formed). Moreover, depending on the characteristic of a raw material (plastic), even if the contact angle of the water of a film surface becomes less than 65 degrees, you may surface-treat and make contact angle of water smaller. Examples of the surface treatment for hydrophilization include antistatic treatment, plasma treatment, corona treatment, and easy adhesion treatment.

The antistatic treatment, the corona treatment, and the easy adhesion treatment can be applied to a method known in the art. Examples of the antistatic treatment include polyvinyl alcohol, polyester, acrylic polymer, polyurethane, and the like. Treatment of coating the surfactant used in the coating, formation of a metal oxide thin film such as depositing a metal oxide or ITO (indium tin-doped indium oxide) and the like, and the like, and easy adhesion treatment, for example, polyvinyl alcohol, poly The process which apply | coats ester, an acrylic polymer, a polyurethane, etc. are mentioned.

Moreover, as a base material which has a surface whose contact angle of water is less than 65 degrees, it is commercially available as T100N38, T100C38 (above, a brand name, Mitsubishi Chemical Polyester Co., Ltd. make), for example.

In addition, one surface (adhesive layer to-be-formed surface) of a base material may surface-treat with the intention of improving adhesiveness with an adhesion layer, etc. Examples of the surface treatment include corona treatment, easy adhesion treatment, antistatic treatment, and the like. In addition, such corona treatment, easy adhesion treatment, and antistatic treatment can be applied to a method known in the art. The thickness of a base material is 10-300 micrometers normally, From a viewpoint of flexibility, etc., Preferably it is 20-100 micrometers, More preferably, it is 25-50 micrometers.

(Adhesive layer)

As an adhesive used for formation of an adhesion layer, when an adhesive layer is formed, it can be re-peeled, and the contact angle of the water in the adhesion layer side is less than 100 degrees (preferably less than 90 degrees, More preferably, less than 80 degrees) The adhesive which can be used) is selected. If this contact angle is 100 degrees or more, wettability with the thin film formation material in the masking tape side surface becomes inadequate, and the height of the meniscus of the thin film formation material formed in the side part (side side vicinity) of a tape cannot be made small, and a thin film The thickness and the coating shape of are different from the desired state. In addition, if the contact angle of water is too small, for example, when the coating liquid is applied in a stripe shape, when the coating liquid is adjacent to the pattern, the coating liquid is excessively pulled toward the tape side, so that the thickness of the thin film is It is easy to cause the problem of becoming in a different state, and it is preferable to set it to 10 degrees or more (preferably 15 degrees or more, more preferably 20 degrees or more) from a viewpoint of solving such a problem.

Moreover, since the thickness of an adhesion layer is thin, it is not easy to measure the contact angle of the water of the adhesion layer side directly, but since the adhesion surface and side surface of an adhesion layer are comprised from the same material, in the adhesion surface and side surface of an adhesion layer, It is possible to assume that the contact angle of water is equivalent. Therefore, in this invention, the contact angle of the water in the to-be-adhered surface of an adhesion layer is prescribed | regulated as the contact angle of the water in the side surface of an adhesion layer.

As such an adhesive, a polyester adhesive and an acrylic adhesive are used preferably. As a polyester adhesive, in order to improve wettability, the diol compound chosen from polycarbonate diol, polycaprolactone diol, etc. (The hydroxyl value becomes like this. Preferably it is 35-130KOHmg / g, More preferably, 45-120KOHmg / g And polyesters obtained from dibasic acids selected from sebacic acid, adipic acid, azelaic acid and phthalic acid.

Moreover, polyester which has a side chain containing a hydrocarbon group, and whose number average molecular weight is 5000 or more is also used preferably. In this case, the content rate of the group containing the hydrocarbon group as a side chain is not specifically limited, It can select suitably according to various characteristics, such as adhesiveness, flexibility, heat resistance, or mechanical properties. Polyester can be used individually or in combination of 2 or more types.

The group containing a hydrocarbon group as a side chain (may be referred to as a "hydrocarbon containing group") is not particularly limited as long as the group contains a hydrocarbon group. Therefore, the hydrocarbon-containing group may be a group composed only of a hydrocarbon group, or may be a hydrocarbon-containing group (eg, a hydrocarbon group-oxy group, a hydrocarbon group-oxycarbonyl group, etc.) in a form in which a hydrocarbon group is bonded through a divalent organic group. do. As the hydrocarbon-containing group, a group composed of only a hydrocarbon group (ie, a hydrocarbon group) can be preferably used. Polyester usually has two or more hydrocarbon containing groups in a molecule | numerator. As the plurality of hydrocarbon-containing groups, only one kind of group may be used, or two or more kinds of groups may be used.

Examples of the hydrocarbon group include an alicyclic hydrocarbon group such as an aliphatic hydrocarbon group such as an alkyl group and a cycloalkyl group (for example, a cyclohexyl group), and an aromatic hydrocarbon group such as an aryl group (for example, a phenyl group or a naphthyl group). Any may be sufficient, Preferably it is an aliphatic hydrocarbon group. As an aliphatic hydrocarbon group, an alkyl group can be used preferably. As the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, And alkyl groups having 1 to 20 carbon atoms, such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.

Moreover, as content rate of a hydrocarbon containing group, so that the glass transition temperature (Tg) of polyester or its crosslinked structure may be -10 degrees C or less, Preferably it is -20 degrees C or less (usually to -100 degreeC), and / or It can select suitably so that transparent and liquid polyester may be obtained in 23 degreeC.

The lower limit of the number average molecular weight of the polyester is, for example, 5000, preferably 10000, more preferably 11000, even more preferably 12000, particularly preferably 20000, and the upper limit is, for example, 90000, preferably 80000, More preferably, it is 70000, More preferably, it is 60000. When the number average molecular weight of polyester is 5000 or more, the mechanical strength as an adhesive does not fall easily, or rework property and heat resistance do not fall easily. On the other hand, when it is 90000 or less, especially 80000 or less, formation of an adhesive sheet is comparatively easy. In addition, the minimum of dispersion degree (weight average molecular weight / number average molecular weight) of polyester is 0.5 normally, Preferably it is 1, and an upper limit is 25 normally, Preferably it is 14, More preferably, it is 13. Here, a number average molecular weight says what was measured by GPC (gel permeation chromatography).

Polyester is obtained by esterification of the polyol component and polycarboxylic acid component which have a hydrocarbon side chain group in at least one component. A polyol component and a polycarboxylic acid component can be used individually or in combination of 2 or more types.

Examples of the polyol component having a hydrocarbon-containing group include neopentyl glycol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and 2-methyl-2-propyl-1 , 3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentadiol, 2,4-diethyl- 1,5-pentanediol, 1,3,5-trimethyl-1,3-pentanediol, 2-methyl-1,6-hexanediol, 2-methyl-1,8-octanediol, 2-methyl-1, And diol components having hydrocarbon-containing groups such as 9-nonanediol, dimer diol, and 2-methyl-1,4-cyclohexanediol.

As the polycarboxylic acid component having a hydrocarbon-containing group, for example, methyl succinic acid, ethyl succinic acid, 2,2-dimethyladipic acid, 2,3-dimethyladipic acid, 2,4-dimethyladipic acid, 3,3 Dicarboxylic acid components having hydrocarbon-containing groups such as -dimethyladipic acid, dimer acid, 2-methyl-1,4-cyclohexanedicarboxylic acid and 2-ethyl-1,4-cyclohexanedicarboxylic acid Can be mentioned. As the polycarboxylic acid component having a hydrocarbon-containing group, derivatives of polycarboxylic acids such as acid anhydrides and lower alkyl esters of these polycarboxylic acids can also be used.

At this time, in the range which can maintain the heat resistance of a polyester, adhesiveness, etc. (for example, in the range which can adjust the glass transition temperature of polyester or its crosslinked structure to -10 degrees C or less), another polyol component It is important to use other polycarboxylic acid components.

As another polyol component, For example, ethylene glycol, 1, 3- propylene glycol, 1, 4- butadiol, 1, 5- pentanediol, 1, 6- hexanediol, 1, 8- octanediol, 1, 9 Linear aliphatic diol components such as nonanediol, 1,10-decanediol, 1,18-octadecanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexane Alicyclic diol components, such as diol, etc. are mentioned.

As another polycarboxylic acid component, For example, aliphatic dicarboxylic acid components, such as succinic acid, adipic acid, azelaic acid, sebacic acid, 1,12- dodecanoic acid, 1,14- tetradecane diacid, Alicyclic dicarboxylic acid components such as 2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4 Aromatic dicarboxylic acid components, such as -naphthalenedicarboxylic acid and 4,4'-biphenyl dicarboxylic acid, etc. are mentioned. Moreover, as another polycarboxylic acid component, polycarboxylic acid derivatives, such as acid anhydride and lower alkyl ester by these polycarboxylic acids, can also be used.

The usage-amount of another polyol component and another polycarboxylic acid component can be selected, for example in the range of 0 to 80 weight% with respect to the polyol component and the polycarboxylic acid component whole quantity.

Moreover, as a polyol component, it is also possible to use the commercially available polyesterdiol component, polyetherdiol component, polycaprolactonediol component, etc. in order to obtain the polymer of the target molecular weight easily. Specifically, as polyester diol component, For example, ethylene glycol, diethylene glycol, 1, 4- butanediol, neopentyl glycol, 3-methyl- 1, 5- pentanediol, 2-butyl- 2-ethyl- 1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8- Diol components, such as decane diol and octadecane diol, succinic acid, methyl succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanoic acid, 1,14-tetradecane diacid and these acids Polyester diol etc. which are obtained by dehydrating a dicarboxylic acid component, such as an anhydride or lower alkyl ester, or dicarboxylic acid components, such as a lower alkyl ester, and its derivative in single or mixed state, etc. are mentioned, As a commercial item, For example, For example, the brand name "Kurarepolyol P-510", "Kurarepolyol P-1010" which are polyesterdiol of 3-methyl-1,5-pentanediol and adipic acid, LES, and the like Polyol P-2010 "," Kuraray Polyol P-3010 "," Kuraray Polyol P-5010 "[least, Ltd. Kuraray manufactured.

Examples of the polyetherdiol component include polyethylene glycol obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran and the like, copolyether copolymerized with polypropylene glycol, polytetramethylene glycol, and the like. Examples thereof include trade names "adecapolyether P-400", "adecapolyether P-1000", "adecapolyether P-2000", which are polyetherdiols obtained by adding propylene oxide to propylene glycol. Adeka polyether P-3000 "[above, Asahi telephone industry Co., Ltd. product] etc. are mentioned.

Examples of the polycaprolactone diol component include caprolactone polyester diols obtained by cyclic ester monomer ring-opening polymerization such as ε-caprolactone and σ-valerolactone. Examples of commercially available products include For example, a brand name "plaque cell L205AL", "plaque cell L212AL", "plaque cell L220PL", "plaque cell L230AL" [above, the Daicel Chemical Industry Co., Ltd. product] etc. are mentioned.

In the adhesive composition of this invention, the aliphatic carbonate diol component which has a structural unit represented by a following formula can be used preferably. By using the following diol component, the adhesive composition excellent in heat resistance can be obtained further. In the following formula, R is a C2-C20 linear or branched hydrocarbon group.

As a specific example of such an aliphatic carbonate diol component, Carbonate diol components, such as a propylene carbonate diol, hexamethylene carbonate diol, and 3-methylpentene carbonate diol; Ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, α-methylbutanediol, α-dimethylbutanediol, 1,5-pentanediol , 2-methyl-2,4-pentanediol, 3-methyl 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, cyclobutane- 1,3-di (2-ethanol), 1,4-dihydroxycyclohexane, cyclohexane-1,4-dimethanol, 1,9-nonanediol, 1,10-decanediol, 1,12-dode Candidiol, neopentylglycol, long chain diol containing polyoxyalkylene glycol, polytetramethylene ether glycol, etc. containing alkylene groups having 2 to 9 carbon atoms (preferably 2 to 4), derivatives thereof, and the like Polycarbonate diol component obtained by polycondensation reaction of the same diol and phosgene; Transesterification of the diols with carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dibenzyl carbonate and the like Polycarbonate diol components obtained by condensation; Copolymerized polycarbonate diol component obtained by using 2 or more types of said diols together; Polycarbonate diol component obtained by esterifying the said various polycarbonate diol component and carboxyl group-containing compound; Polycarbonate diol component obtained by etherifying the said various polycarbonate diol component and a hydroxyl group containing compound; Polycarbonate diol component obtained by transesterifying the said various polycarbonate diol component and ester compound; Polycarbonate diol component obtained by transesterifying the said various polycarbonate diol component and a hydroxyl-group containing compound; Modified polyester type polycarbonate diol component obtained by carrying out polycondensation reaction of the said various polycarbonate diol component and dicarboxylic acid compound; The copolymerization polyether type polycarbonate diol component etc. which are obtained by copolymerizing the said various polycarbonate diol component and alkylene oxide are mentioned, As a commercial item of the carbonate diol component used preferably, a brand name "PLACCEL CD205", " PLACCEL CD210 '', `` PLACCEL CD220 '', `` PLACCEL CD205PL '', `` PLACCEL CD210PL '', `` PLACCEL CD220PL '' (above, manufactured by Daicel Chemical Industry Co., Ltd.) -1000 "," PNOC-2000 "(above, Kuraray Co., Ltd.), etc. are mentioned.

Moreover, in the adhesive of this invention, a triol or more polyol component or polyhydric carboxylic acid component can also be added for the reason that the balance of adhesiveness and heat resistance can be caught easily.

Examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolpropane, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, pentaerythritol, and dipenta Aliphatic polyhydric alcohols, such as erythritol, and derivatives thereof are mentioned. Moreover, as a trivalent or more polyhydric carboxylic acid, 1,2, 4- butane tricarboxylic acid, 1,2, 5- hexane tricarboxylic acid, 1,2, 4- cyclohexane tricarboxylic acid, meso -Aromatic polyhydric carboxylic acids such as aliphatic polyhydric carboxylic acids such as butane-1,2,3,4-tetracarboxylic acid, trimellitic acid and pyromellitic acid, acid anhydrides and lower alkyl esters thereof; Can be mentioned.

Moreover, aliphatic dicarboxylic acid and aromatic polyhydric carboxylic acid are mentioned as carboxylic acid normally used as a polyhydric carboxylic acid component. Specifically, aliphatic dicarboxylic acids such as succinic acid, methyl succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanoic acid, 1,14-tetradecane diacid, dimer acid, and phthalic acid And aromatic dicarboxylic acids such as 1,4-naphthalenedicarboxylic acid and 4,4'-biphenyldicarboxylic acid, and acid anhydrides and lower alkyl esters thereof.

As for the usage-amount of a trivalent or more polyhydric alcohol and / or a trivalent or more polyhydric carboxylic acid, the optimal usage amount is selected according to the molecular weight and valence so that the dispersion degree (weight average molecular weight / number average molecular weight) of polyester may be an appropriate value. do. Usually, it is good to set it as the ratio which becomes 2-30 weight%, Preferably it is 4-15 weight% with respect to the total amount of aliphatic diol and dicarboxylic acid. When the amount of the trivalent or higher polyhydric alcohol and / or the trivalent or higher polyhydric carboxylic acid is less than 2% by weight, the dispersion of the polyester tends to be small. It becomes large and these cases may cause the trouble mentioned later easily.

In the case of using a trivalent or higher polyhydric alcohol and / or a trivalent or higher polyhydric carboxylic acid, the polyester has a degree of dispersion (weight average molecular weight / number average molecular weight) of 2.2 or more, preferably 2.5 or more, and more preferably 2.7 or more. . As an upper limit, Preferably it is 25 or less, More preferably, it is 20 or less, More preferably, it is 14 or less, Especially preferably, it is 13 or less. As already described, the dispersion degree of polyester can be adjusted with the usage-amount and number average molecular weight of a trivalent or more polyhydric alcohol and / or a trivalent or more polyhydric carboxylic acid, and it is suitable according to a use purpose within the said range. This is done by adjusting the dispersion degree. If the degree of dispersion is less than the lower limit, it is difficult to balance mechanical strength and flexibility, and there is a tendency that both heat resistance and adhesion to roughing are not achieved. Moreover, when dispersion degree is too big | large, since polyester becomes high viscosity and gelatinization occurs easily and it becomes difficult to form an adhesive sheet, it is preferable to carry out in the said range.

In addition, a weight average molecular weight and a number average molecular weight say what was obtained by measuring by GPC (gel permeation chromatography).

A polyester-based adhesive can be obtained by esterifying using such a polyol component or a polycarboxylic acid component using an appropriate catalyst or the like. In this reaction, the polyol component and the polycarboxylic acid component are preferably in an equimolar reaction, but in order to promote the ester reaction, either of them may be used excessively. In such an adhesive composition, the function as an adhesive agent can be expressed effectively by crosslinking polyester. Although it does not specifically limit as a crosslinking processing method which crosslinks polyester, For example, The compound which has a functional group which can react with a hydroxyl group and / or a carboxyl group in polyester (for example, a polyisocyanate compound, an epoxy compound, The crosslinking agent of an aziridine compound, etc.) can be added, and the method of using what is called a crosslinking agent can be employ | adopted preferably. As a crosslinking agent, as mentioned above, although a polyisocyanate compound, an epoxy compound, an aziridine compound, etc. are mentioned, A polyisocyanate compound can be used especially preferably. A crosslinking agent can be used individually or in combination of 2 or more types.

As a polyisocyanate compound as a crosslinking agent, For example, Lower aliphatic polyisocyanates, such as tetramethylene diisocyanate and hexamethylene diisocyanate; Alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; Aromatic diisocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate; Trimethylolpropane / tolylene diisocyanate trimer adduct (for example, brand name "Colonate L" Nippon Polyurethane Industry Co., Ltd. product), trimethylolpropane / hexamethylene diisocyanate trimer adduct (for example, Isocyanate addition products, such as "colonate HL" and Nippon Polyurethane Industry Co., Ltd.), etc. are mentioned.

The usage-amount of a crosslinking agent is suitably selected according to the molecular weight balance of polyester which should be bridge | crosslinked, Furthermore, according to the use use etc. as an adhesive. As a use use of a crosslinking agent, it is generally 0.5 weight part or more with respect to 100 weight part of polyester. As a crosslinking agent, it is preferable to use it at the usage-amount which becomes 10 weight% or more (preferably 20 weight% or more) of the solvent insoluble component after crosslinking process of polyester. In addition, the detail of the solvent insoluble component after the crosslinking process of polyester is mentioned later. As described above, in the present invention, in order to achieve both mechanical strength and flexibility (or both of heat resistance and adhesiveness), it is not necessary to strictly adjust the amount of the crosslinking agent, so that the crosslinking treatment of the polyester can be easily performed.

Moreover, an electron beam curable compound (polyfunctional monomer) can be used as a substantially crosslinking agent. This polyfunctional monomer is a compound which has a some unsaturated bond in 1 molecule, and can generate a crosslinking reaction by an electron beam etc. As such a polyfunctional monomer, a (meth) acrylate type polyfunctional monomer can be used preferably. Examples of the (meth) acrylate-based polyfunctional monomers include polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol mono. Hydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butylene glycoldi ( Meth) acrylate, 1,6-hexanedioldi (meth) acrylate, and the like. A polyfunctional monomer can be used individually or in combination of 2 or more types.

The usage-amount of the said polyfunctional monomer is suitably selected according to the balance with polyester which should be bridge | crosslinked like a crosslinking agent, and also according to the use use as an adhesive etc. Generally the usage-amount of a polyfunctional monomer is 1 weight part or more with respect to 100 weight part of polyester, and it uses 10 weight% or more of the solvent insoluble component after the crosslinking process of polyester by using it in this ratio and crosslinking with an electron beam. 20 wt% or more). Thus, in order to improve the function as an adhesive by the crosslinking of polyester, it is preferable that it is 10 weight% or more (preferably 20 weight% or more) as a solvent insoluble component after the crosslinking process of polyester. When the solvent insoluble component after crosslinking process of polyester is less than 10 weight%, the cohesion force of an adhesive may be insufficient, mechanical strength may fall, and sufficient heat resistance may not be obtained. Moreover, when the solvent insoluble component after crosslinking process of polyester exceeds 70 weight%, the softness | flexibility of the crosslinked body of polyester will be impaired, and adhesiveness will fall easily, so as an upper limit of the solvent insoluble component after crosslinking process of polyester. Is preferably 70% by weight (preferably 60% by weight).

Moreover, as a solvent in the solvent insoluble component after a polyester crosslinking process, it can select suitably according to a use purpose etc., For example, Aromatic hydrocarbons, such as toluene and xylene; Aliphatic hydrocarbons such as hexane; Alicyclic hydrocarbons such as cyclohexane; Alcohols such as methanol and ethanol; Esters such as ethyl acetate; Ketones such as methyl ethyl ketone; Glycols such as ethylene glycol; Glycol ether, such as propylene glycol monoethyl ether, etc. can be used.

In addition, the glass transition temperature of polyester or crosslinked polyester is -10 degrees C or less (for example -100 degreeC --10 degreeC), Preferably it is -20 degrees C or less (for example -100 degreeC --20) Is preferred). When the glass transition temperature after crosslinking process of polyester or polyester exceeds -10 degreeC, the crosslinked structure of polyester becomes hard, flexibility falls, and adhesiveness falls. In addition, as the glass transition temperature, the glass transition temperature in the crosslinked structure after the crosslinking process of polyester is usually employ | adopted, and it is employ | adopted similarly in this specification also.

Moreover, it is preferable to contain the acrylic polymer which contains a (meth) acrylic-acid alkylester and a hydrophilic monomer as a monomeric unit as an acrylic adhesive. The alkyl group of the (meth) acrylic acid alkyl ester is preferably 2 to 14 carbon atoms, and may be in any of linear, branched and cyclic forms. Examples of such alkyl groups include ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, isoamyl group, hexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, isononyl group and isode Practical skills etc. are mentioned. Especially, a C2-C10 alkyl group is preferable and a C4-C8 alkyl group, such as a butyl group and 2-ethylhexyl group, is more preferable. If carbon number is out of the said range, adhesive force will become inadequate and it will become difficult to function as an adhesive. In addition, the said (meth) acrylic-acid alkylester can be used 1 type or in combination of 2 or more types.

The hydrophilic monomer is not particularly limited as long as it has a hydrophilic group such as a hydroxyl group, an amino group, an amide group, a sulfonic acid group, a carboxyl group, an acid anhydride group, an imide group, a phosphoric acid group, or an alkylene oxide group in the molecule. Specifically, 2-hydroxyethyl (meth) acrylic acid, 2-hydroxypropyl (meth) acrylic acid, 2-hydroxybutyl (meth) acrylic acid, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (Meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl Acrylate, N-methylol (meth) acryl amide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, 3-hydroxypropyl (meth) Acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxy Such as oxydecyl (meth) acrylate and 12-hydroxylauryl (meth) acrylate Acid group-containing monomers; Amino group-containing monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate; (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, Amide group-containing monomers such as N-butoxymethyl (meth) acrylamide, N, N, -methylenebis (meth) acrylamide, N-isopropylacrylamide and N, N-dimethylaminopropylacrylamide; Contains sulfonic acid groups such as styrenesulfonic acid, allylsulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidepropanesulfonic acid, sulfopropyl (meth) acrylate, and (meth) acryloyloxynaphthalenesulfonic acid Monomers; Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; Imide group-containing monomers such as cyclohexyl maleimide, isopropyl maleimide, N-cyclohexyl maleimide, itaciconimide and N-phenylmaleimide; Phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate; In addition, (meth) acrylonitrile, N- (meth) acryloyl morpholine, N-vinyl-2-pyrrolidone, N-vinyl caprolactam, etc. are mentioned. These can be used 1 type or in combination of 2 or more types.

As an oxyalkylene unit of an alkylene oxide group containing monomer, what has a C1-C6 alkylene group is mentioned, For example, an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxybutylene group, etc. are mentioned. Can be. The hydrocarbon group of the oxyalkylene chain may be linear or may be branched.

Moreover, as an average addition mole number of the oxyalkylene unit with respect to the said alkylene oxide group containing monomer, it is preferable that it is 3-40 from a viewpoint of wettability with a to-be-adhered body, It is more preferable that it is 4-35, 5-30 Is particularly preferred. Since the average added mole number is greater than 3, better wettability with the adherend is obtained. In addition, when the average added mole number is greater than 40, the contamination on the adherend tends to increase. In addition, the terminal of an oxyalkylene chain may remain a hydroxyl group, or may be substituted by the other functional group. Moreover, it is preferable that the said alkylene oxide group containing monomer is a monomer which has an ethylene oxide group. By using the (meth) acryl monomer which has a monomer which has an ethylene oxide group, better wettability with a to-be-adhered body is easy to be obtained. As a specific example of the (meth) acrylic-acid alkylene oxide adduct, For example, polyethyleneglycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethyleneglycol-polypropylene glycol (meth) acrylate, polyethyleneglycol- Polybutylene glycol (meth) acrylate, polypropylene glycol polybutylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth ) Acrylate, octoxy polyethylene glycol (meth) acrylate, lauoxy polyethylene glycol (meth) acrylate, stearoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (Meth) acrylate, octoxy polyethylene glycol-polypropylene glycol (meth) It may include methacrylate and so on.

In order to make the acrylic adhesive which the contact angle of water can provide the adhesion layer of the said range, For example, 70-100 weight part (preferably 70-80 weight part) of alkyl (meth) acrylates, and 1-30 hydrophilic monomers It is preferable to contain an acrylic polymer obtained from parts by weight (preferably 20 to 30 parts by weight), and in this case, 2-hydroxyethyl (meth) acrylate and N- (meth) acryloyl morpholine as hydrophilic monomers. And it is preferable to use in combination any 1 type or 2 or more types chosen from (meth) acrylamide. Moreover, the acrylic polymer obtained from 70-80 weight part of 2-ethylhexyl acrylates, and the acrylic polymer obtained from 20-30 weight part of hydrophilic monomers, and the acrylic polymer obtained from 90-100 weight part of butyl acrylates, and 1-10 weight part of hydrophilic monomers It is also preferable to contain the. In addition, a polymerization method is not specifically limited, For example, normal polymerization methods, such as solution polymerization and emulsion polymerization, can be employ | adopted. In addition, as a polymerization initiator, well-known polymerization initiators, such as an azo initiator and a peroxide initiator, can be used, for example. The weight average molecular weight (Mw) of the acrylic polymer obtained in this way is 300,000-2 million normally, Preferably it is 500,000-11.7 million. When Mw is less than 300,000, cohesion force as an adhesive becomes difficult to be obtained, and heat resistance and durability tend to fall, while when it exceeds 2 million, it becomes high viscosity and it becomes difficult to form an adhesive sheet.

After the masking tape is produced, the side surface of the masking tape is surfaced so that the contact angle of water on the side of the adhesive layer is less than 100 ° and the contact angle of water on the side of the adhesive layer with water is less than 100 °. You may process it. Examples of such surface treatment include easy adhesion treatment and application of a hydrophilic material (for example, a photocatalyst). Examples of the photocatalyst include titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), and bismuth oxide (Bi ₂ O _3). And optical semiconductors such as iron oxide (Fe ₂ O ₃ ), and these can be used alone or in combination of two or more thereof. In addition, there are anatase type and rutile type in titanium oxide, and both can be used in this embodiment, but an anatase type is preferable. By using such a photocatalyst, the wettability of a base material becomes still higher and a thin film with a uniform film thickness can be obtained more reliably.

Moreover, a crosslinking agent and surfactant can be contained in an adhesive as needed. As a crosslinking agent, the crosslinking agent normally used in the said technical field can be used, For example, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an oxazoline type crosslinking agent, an aziridine type crosslinking agent, a metal chelate type crosslinking agent, etc. are mentioned. Especially, an isocyanate type crosslinking agent and an epoxy type crosslinking agent are preferable. The compounding quantity of such a crosslinking agent is 0.01-10 weight part normally with respect to 100 weight part (solid content) of the said polymer component, Preferably it is 1-6 weight part. When the amount of the crosslinking agent is too small, the crosslinking density decreases and it is difficult to obtain sufficient strength. On the other hand, when the amount of the crosslinking agent is too large, the adhesive force is lowered or the workability at the time of production tends to be inferior. Moreover, as surfactant, nonionic surfactant, such as polyoxyethylene polyoxypropylene glycol, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, and polyoxyethylene fatty acid ester, is mentioned. Among them, polyoxyethylene polyoxypropylene glycol is preferred because of less bubbles and the surface can be cleaned, and commercially available as EPAN (trade name, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.). The compounding quantity of such surfactant is 0.001-1 weight part normally with respect to 100 weight part (solid content) of the said polymer component, Preferably it is 0.01-0.1 weight part.

In addition, a tackifier, an antioxidant, a filler, a pigment, a coloring agent, etc. may be added to the adhesive as needed. Examples of the tackifier include rosin resins, terpene resins, aliphatic petroleum resins, aromatic petroleum resins, copolymerized petroleum resins, and alicyclic petroleum resins.

(2nd embodiment)

FIG.2 (b) is sectional drawing which shows the masking tape for board | substrates which concerns on 2nd Embodiment. The masking tape 20 for board | substrates which concerns on this embodiment differs from the masking tape 10 for board | substrates which concerns on said 1st Embodiment by the point that the separator 5 is formed in the to-be-adhered surface of the adhesion layer 3. The structure of the base material 1 and the adhesion layer 3 is as having demonstrated in the said embodiment. In addition, a separator can be attached suitably according to a use purpose. As a separator, what was illustrated by the said description is mentioned. In order to improve the peelability from an adhesion layer, the surface of a separator may perform mold release processes, such as a silicone process, a long chain alkyl process, and a fluorine process, as needed. Moreover, the thickness of a separator is 10-300 micrometers normally, Preferably it is 20-100 micrometers, More preferably, it is 38-75 micrometers.

Next, the manufacturing method of the masking tape for board | substrates of this invention is demonstrated. Generally, the masking tape for a board | substrate apply | coats the said adhesive to a base material, and forms an adhesive layer by drying, or apply | coats the said adhesive on another base material, such as a release paper, and dries to form an adhesive layer, and this is then made to a base material. It can manufacture by bonding. In addition, after the masking tape for board | substrates shown in FIG. 1 forms an adhesion layer on one side of a base material, it can manufacture by winding up the surface of an adhesion layer in the roll form overlapping with the other side of a base material. Moreover, when apply | coating an adhesive on a base material, a conventional coater, for example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a fountain die coater etc. Can be used. In this case, an adhesive is apply | coated so that the thickness of the adhesion layer after drying may be about 3-100 micrometers normally, Preferably it is about 5-60 micrometers, More preferably, it is about 10-40 micrometers.

The masking tape for a board | substrate of this invention apply | coats a thin film, for example by apply | coating fluid materials, such as an organic EL material and an electroconductive material one by one, for example, a nozzle coating method, to an organic EL board | substrate, and apply | coats an organic ELD In the manufacturing process of the organic ELD (display panel) which produces a (display panel), it adheres to the application | coating unnecessary area | region on a board | substrate, and is used before application | coating of a fluid material.

By using the masking tape for a substrate of the present invention, the thin film (film) of the flowable material applied around the tape (side) does not cause an increase in the undesired thickness, and is caused by the undesired increase of the thin film (film). The problem which arises (for example, disconnection of the negative electrode in organic ELD, the fall of moisture or oxygen barrier property from the outside in a negative electrode, etc.) can be avoided.

The above-mentioned "organic EL material" is, for example, polyparaphenylene vinylene (PPV), polyparaphenylene vinylene derivative, polythiophene (PAT), polythiophene derivative, fluorene derivative, polyparaphenylene Known light emitting polymers such as (PPP), polyparaphenylene derivatives, carbazole derivatives, and polysilane-based polymers refer to dispersions or solutions dispersed or dissolved in a solvent, and the term "conductive material" refers to polyethylene dioxythiophene (PEDOT). ) -Polystyrenesulfonic acid (PSS), polyaniline (PA) -PSS, PTPDES (ie, formula:

Well-known conductive polymers, such as a polymer), disperse | distribute to the solvent, or the dispersion liquid or solution which it points out. These dispersions or solutions generally contain a light emitting polymer or a conductive polymer in a concentration of at least 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more.

One embodiment in the case of producing organic ELD using the masking tape for board | substrates of this invention is as follows.

The organic ELD according to the present aspect includes a pair of opposing electrodes and one or more organic layers disposed between the electrodes.

First, a substrate is prepared. As a board | substrate, transparent substrates, such as a glass substrate and a plastic substrate, are used, for example. The substrate may be patterned by, for example, ITO (indium tin oxide) or the like. Subsequently, the application unnecessary area | region (thin film non-formation area | region) of a board | substrate is masked with the masking tape for substrates of this invention at room temperature-80 degreeC.

Next, a coating liquid obtained by dispersing polyethylenedioxythiophene-polystyrenesulfonic acid (PEDOT-PSS) in water is applied to the substrate by a nozzle coating method to form a uniform thin film having a thickness of about 50 nm to 100 nm.

Subsequently, after peeling the masking tape for a board | substrate, after heat-drying a board | substrate or heat-drying a board | substrate, the board | substrate masking tape is peeled off and a hole transport layer is formed.

Subsequently, the application | coating unnecessary area | region (thin film non-formation area | region) of a board | substrate is masked with the masking tape for substrates of this invention at room temperature or 80 degreeC.

Subsequently, after apply | coating organic electroluminescent material (R, G, B) to a board | substrate by a nozzle coating method, peeling off the masking tape for board | substrates, a board | substrate is heat-dried or a board | substrate is heat-dried, and then The masking tape is peeled off to form a uniform light emitting layer having a thickness of about 60 to 80 nm.

Subsequently, the substrate is moved into a vacuum evaporator to form a cathode having a thickness of about 100 to 300 nm on the light emitting layer by vapor deposition. And the adhesive part of the masking tape for board | substrates is sealed with an adhesive agent. In this way, organic ELD is obtained.

The masking tape for a board | substrate of this invention is not limited to use in the manufacturing process of organic ELD as mentioned above, It is applicable also in manufacturing processes, such as a liquid crystal, an organic thin film solar cell, a plasma display. That is, not only an organic EL board | substrate but a board | substrate at the time of apply | coating and forming the thin film (coating film) of a fluidic material to various board | substrates, such as a liquid crystal substrate, an organic thin film solar cell substrate, a plasma display substrate, a semiconductor wafer, and an optical disk substrate. It can use suitably as a masking tape which masks the application unnecessary area | region of an image.

Moreover, the masking tape for board | substrates of this invention is a manufacturing process which has at least the application | coating process to the board | substrate of the fluid material which consists of a solution or dispersion liquid using an aqueous solvent (manufacturing processes, such as an organic ELD, a liquid crystal, an organic thin film solar cell, a plasma display, etc.). ) Is particularly preferred. That is, when forming the thin film by apply | coating the fluid material using an aqueous solvent, the increase of the unwanted thickness in the thin film (coating film) of the fluid material apply | coated around the tape (side part) can be suppressed especially effectively. The term "aqueous solvent" as used herein means a solvent mainly composed of water or water, and specifically, in general, water, pure water, distilled water, ion-exchanged water, or the like, or less than 50% by weight with respect to water. And an aliphatic alcohol having 1 to 7 carbon atoms (preferably 1 to 4 carbon atoms), or a mixture of hydrophilic organic solvents such as acetone.

The masking tape for a board | substrate of this invention is not only used when forming a thin film on a board | substrate by a nozzle coating method, but is applicable also when forming a thin film on a board | substrate by other well-known methods, such as an inkjet method and a spin coat method. Do.

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

(Preparation of Adhesive)

(Manufacture example 1)

In a four-necked separating flask equipped with a stirrer, a thermometer, and a reaction byproduct separation tube, polycarbonate diol (trade name: PLACCEL CD220PL, hydroxyl value: 55.1KOHmg / g, manufactured by Daicel Chemical Industry Co., Ltd.) 200.0 parts by weight, sebacic acid 19.8 parts by weight and 0.1 part by weight of tetra n-butyltitanate as a catalyst were injected, and a small amount of xylene was added as a solvent for discharging water, which is a reaction byproduct. Subsequently, the reaction solution was stirred to raise the temperature to 180 ° C, and the mixture was constantly stirred at this temperature. After a while, the outflow separation of water was confirmed, and after confirming that the reaction began to proceed, the mixture was heated and stirred for about 18 hours. And the weight average molecular weight 49,000 and polyester of dispersion degree 1.8 were obtained.

Next, 3.5 weight part of isocyanate type crosslinking agents (brand name: Colonate HL, Nippon Polyurethane Industry Co., Ltd. product) was added with respect to 100 weight part of obtained polyester, and the polyester adhesive was obtained.

(Manufacture example 2)

In the same reaction vessel as in Production Example 1, 75 parts by weight of acrylic acid 2-ethylhexyl (2-EHA), 25 parts by weight of N-acryloyl morpholine (ACMO), 3 parts by weight of acrylic acid (AA), and 2-acid acrylic acid 0.5 weight part of oxyethyl (HEA) was injected | poured, and normal solution (ethyl acetate) polymerization was performed, and the acrylic polymer of the weight average molecular weight 1,100,000 was obtained.

Subsequently, with respect to 95 weight part of obtained acrylic polymer, 1.5 weight part of epoxy type crosslinking agents (brand name: Tetrad C, Mitsubishi Gas Chemical Industry Co., Ltd. product), an isocyanate type crosslinking agent (brand name: Colonate L, Nippon Polyurethane Industry Co., Ltd.) ) Manufacturing) 2 weight part and 0.05 weight part of nonionic surfactants (brand name: Epan710, Daiichi Kogyo Pharmaceutical Co., Ltd. product) were added, and the acrylic adhesive (henceforth "acrylic adhesive A") was obtained.

(Manufacture example 3)

90 weight part of 2-EHA and 3.5 weight part of HEA were injected into the reaction container similar to the manufacture example 1, and normal solution (ethyl acetate) superposition | polymerization was performed and the acrylic polymer with a weight average molecular weight of 600,000 was obtained.

Subsequently, 3.5 weight part of isocyanate type crosslinking agents (Nippon Polyurethane Industry Co., Ltd. product, Colonate HX) was added with respect to 100 weight part of obtained acrylic polymers, and the acrylic adhesive (henceforth "acrylic adhesive B") was obtained.

(Manufacture example 4)

Silicone polymer with 60% solids (polymer name: KR-3770, Shin-Etsu Chemical Co., Ltd.) in 70 parts by weight of a silicone polymer with 60% solids (trade name: X-40-3229, manufactured by Shin-Etsu Chemical Co., Ltd.) 30 parts by weight, 0.5 parts by weight of a catalyst having a solid content of 5% (trade name: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 parts by weight of toluene were added to obtain a silicone pressure sensitive adhesive.

(Manufacture example 5)

95 parts by weight of butyl acrylate (BA) and 5 parts by weight of acrylic acid (AA) were injected into the same reaction vessel as in Production Example 1, and a conventional solution (ethyl acetate) polymerization was performed to obtain an acrylic polymer having a weight average molecular weight of 600,000.

Next, with respect to 100 weight part of obtained acryl-type polymers, 4.5 weight part of epoxy type crosslinking agents (brand name: Tetrad C, Mitsubishi Gas Chemical Industries, Ltd.), an isocyanate type crosslinking agent (brand name: Colonate L, Nippon Polyurethane Industry Co., Ltd.) (Manufacture) 1 weight part was added, and the acrylic adhesive (henceforth "acrylic adhesive C") was obtained.

(Example 1)

The polyester-type adhesive obtained by the manufacture example 1 was apply | coated so that thickness might be set to 15 micrometers, and it dried on the conditions of 130 degreeC * 3min on the silicone process surface of the following silicone processing separator. Masking by adhering the corona treated surface of the polyester film (brand name: T100N38, 38 micrometers in thickness, Mitsubishi Chemical Polyester Co., Ltd.) which has an antistatic layer on one side, and a corona treated surface on the other side to the adhesive surface after drying I got a tape. The obtained masking tape was mounted on the smooth glass plate, it cut on the base material side with the razor for trimming, and it was set as the sample. In addition, the trimming razor shall not use the knife used once.

<Production of Silicon Treated Separator>

(Production made of release coat)

Polydimethylsiloxane (trade name: KS-3601, manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts by weight of acetylene-based reaction control agent (trade name: CAT PLR-1, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by weight , Acetylene reaction control agent (trade name: CAT PLR-2, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight, solvent (trade name: normal hexane, manufactured by Maruzen), solvent (trade name: normal heptane, Toa Synthesis Co., Ltd. was added and stirred for 20 minutes, and 5 parts by weight of a catalyst (trade name: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred for 10 minutes. Got it.

(Production of release film)

Release polyester by apply | coating the said silicone coating liquid to the corona treatment surface of single-sided corona treated polyester film (brand name: S-105, thickness 50 micrometers, Toray Corporation make) by the gravure method, and drying at 140 degreeC x 1min. A film (weight 0.07 g / cm 2 after drying of the silicone release layer) was obtained.

(Example 2)

Using the acrylic adhesive A obtained in the manufacture example 2, the masking tape was obtained by the method similar to Example 1 except having changed the dry conditions of adhesive to 140 degreeC x 3min.

(Example 3)

The base material adhere | attached on an adhesive surface is made into the polyester film (brand name: S-10, thickness 38 micrometers, Toray Corporation make), and a backing treatment agent (brand name: alcoholic backing treatment agent, Marusho Industrial Co., Ltd.) is formed on the back of masking tape. ) And the photocatalyst (brand name: M-5 type alcohol solvent, the Marusho Industrial Co., Ltd. product) were apply | coated and the masking tape was obtained by the method similar to Example 2.

(Example 4)

Using acrylic adhesive B obtained in Production Example 3, drying conditions of the adhesive were 130 ° C. × 1 min, and cut in the same manner as in Example 1 with a knife for trimming, and then on the side of the masking tape, a base treatment agent (brand name: alcohol-based base treatment agent) The masking tape was obtained by the method similar to Example 1 except having apply | coated and the photocatalyst (brand name: M-5 type alcohol solvent, the Marusho Industrial Co., Ltd. product) and photocatalyst were applied.

(Example 5)

Using the acrylic adhesive C obtained in the manufacture example 5, the masking tape was obtained by the method similar to Example 1 except having changed the drying conditions of the adhesive to 140 degreeC x 3min.

(Comparative Example 1)

Using the acrylic adhesive B obtained in the manufacture example 3, the masking tape was obtained by the method similar to Example 1 except having set the drying conditions of adhesive to 130 degreeC x 1min.

(Comparative Example 2)

On the corona treated surface of the polyester film (brand name: T100N38, thickness 38micrometer, Mitsubishi Chemical Polyester Co., Ltd.) which has an antistatic layer on one side, and a corona treated surface on the other side, the following priming agent and manufacture example 4 The silicone pressure-sensitive adhesive obtained in the above was applied in sequence, and the drying conditions of the priming agent were 120 ° C. × 2 min, and the drying condition of the adhesive was 100 ° C. × 5 min, and a polyester film (brand name: S-10, thickness 38 μm, dore) was used on the adhesive face. Masking tape was obtained by the method similar to Example 1 except having adhere | attached (manufacture).

<Preparatory preparations>

Catalyst of 5% of solid content (brand name: CAT-PL-50T, Shin-Etsu Chemical Industry) in 100 weight part of silicone polymer of 30% of solid content (brand name: X-40-3501, manufactured by Shin-Etsu Chemical Co., Ltd.) Note) 0.5 part by weight, 130 parts by weight of hexane, and 130 parts by weight of methyl ethyl ketone were added to obtain a primary agent.

(Comparative Example 3)

The masking tape was obtained by the method similar to Example 2 except having made the base material adhere | attached on an adhesive face into the polyester film (brand name: S-10, thickness 38 micrometers, Toray Corporation make).

(Comparative Example 4)

The base material adhere | attached on an adhesive surface was made into the polypropylene / polyethylene blend film (polypropylene: polyethylene = 90: 10 (weight ratio)) which corona-treated on one side, and thickness is 40 micrometers, and the corona treated surface was adhere | attached on the adhesive A masking tape was obtained in the same manner as in Example 2 except for the above.

[Evaluation test]

(1) contact angle of water

After the masking tape was fixed flat on the glass plate with the test surface facing up, 3 μg of distilled water was attached to the test surface with a glass syringe equipped with a stainless steel needle having an internal diameter of 0.4 mm. Within 20 seconds after attachment, the contact angle was measured by a θ / 2 method by a contact angle meter (trade name: CA-X type, manufactured by Kyowa Interface Science Co., Ltd.) under 23 ° C x 50% RH. 10 points of contact angles were measured and it was set as the average value remove | excluding two points of top and bottom. In addition, since the contact layer side is thin and direct contact angle cannot be measured, when there is a separator in a masking tape, the contact angle in the adhesion surface of the adhesion layer which peeled the separator as mentioned above was measured, It was set as the contact angle of water in. In addition, when the masking tape full surface contacts the masking tape back surface and becomes a winding body, the contact angle in the adherend surface of the adhesion layer which peeled the masking tape from the masking tape back surface was measured, and the water of the side of an adhesive layer was measured. It was set as the contact angle. In the case of Example 4 which apply | coated the photocatalyst to the masking tape side surface, the photocatalyst was apply | coated similarly to the to-be-adhered surface on which the separator was peeled off, and it was set as the contact angle of the water in the side of an adhesion layer by measuring the contact angle of the surface. The evaluation results are shown in Table 1.

(2) wettability test on the masking tape side

Tilt the glass so that toluene does not accumulate in the same place on the non-tin contact surface of the glass (1.3 mm x 65 mm x 165 mm micro slide glass, manufactured by Matsunami Co., Ltd.), and toluene flows and washes so that toluene does not touch other than glass, A masking tape is attached to the naturally dried surface, and a stainless steel needle with an internal diameter of 0.8 mm is mounted on a water dispersion type conductive material (trade name: Bayer P VP CH 8000, manufactured by Bayer Co., Ltd.) at a place 1 mm away from the measurement surface. 0.5 μg was attached by one glass syringe. It left to stand at 23 degreeC x 50% RH for 24 hours, the masking tape was peeled after that, and the width | variety of the electrically conductive material extended to the masking tape side surface was measured. The width was made into the average value measured 5 points. That is, FIG.3 (a) attaches the masking tape T, dripping the water dispersion liquid conductive material 32, and left the measurement surface 31 of the glass plate 30 at the time left to stand for 24 hours. It is a schematic diagram observed, and FIG.3 (b) is a schematic diagram of the state which peeled masking tape T after leaving for 24 hours. Said "width of the conductive material extended to the masking tape side surface" is the width | variety of the largest width part W1 of the side which contacted the masking tape T of the conductive material 32 in the state of FIG.3 (b).

It was judged that the width W1 of the flowable material measured in this way was larger than 3 mm, and it was judged that the width was 3 mm or less.

 The evaluation results are shown in Table 1.

(3) wettability test on masking tape back

The masking tape was fixed with the test surface facing up on a smooth plate, and a 2 mL polyethylene dropper (trade name: Code No. 1-4656-01, manufactured by Azwan Co., Ltd.) was used as a conductive material of water dispersion type (product name). : 1 drop of Bayer P VP CH 8000, manufactured by Bayer Co., Ltd. was added dropwise to the test surface, and evaluated as to whether or not the conductive material rolled down when tilted at 45 °. The evaluation results are shown in Table 1.

Good (○): It does not roll down.

Poor (×): Rolls down.

(4) the height of the thin film at the masking tape side

The height of the thin film in the masking tape side part was measured by the following method.

First, after forming an ITO film on a glass substrate or a transparent plastic substrate, the ITO film is patterned using photolithography technique to form a plurality of stripe-shaped first electrodes. This first electrode corresponds to the anode.

Next, an electrically insulating partition (bank) is formed using photolithography or the like to fill the spaces between the first electrodes. As a material of a partition, inorganic materials, such as organic materials, such as an acrylic resin, an epoxy resin, and polyimide, and liquid glass, are used, for example.

Next, a masking tape is adhered on the ITO film, and then a water dispersion liquid conductive material (trade name: Bayer P VP CH 8000, manufactured by Bayer Corporation) is supplied (coated) between the partition walls. Supplying between the partitions of the conductive material at this time is performed using the coating apparatus described in JP-A-2002-75640.

After the application | coating process, a hole transport liquid is supplied between each partition by the same apparatus, a solvent is removed from a hole transport liquid, and post-baking is performed for 5 to 10 minutes at 100 degreeC, and a hole transport layer is formed. Moreover, the application amount of an electroconductive material is set so that the film thickness of a positive hole transport layer may be several tens-several hundred nm.

Next, the masking tape was peeled off, and the height from the ITO film of the peeling end faced to the tape side of the hole transport layer was used as a step, surface roughness, and micro shape measuring device P-11 (manufactured by KLA-Tencor Co., Ltd., brand name). Measure by

The case where this height was 5 micrometers or less was made into favorable ((circle)), and when larger than 5 micrometers was determined as defect (x).

The organic EL element supplies an organic EL material to form an organic EL layer via a hole transporting layer on the first electrode, and after completion of the formation of the organic EL layer, the organic EL element is orthogonal to the first electrode and faces the second electrode. It is produced by forming a plurality of electrodes in parallel or on the entire surface by a vacuum deposition method or the like. In the case of depositing the second electrode by the CVD apparatus, the peeling end of the hole transporting layer should be smaller than 5 µm, which is the upper limit of deposition by the CVD apparatus, and the peeling end of the hole transporting layer protrudes from the second electrode. Therefore, it evaluated whether the height of the peeling edge part of a positive hole transport layer is set to 5 micrometers or less.

In general, since the film thickness of the hole transport layer is an ultra-thin film of several tens of nm to several hundred nm, the height of the peeled end of the hole transport layer is the same as the film thickness of the hole transport layer, but the smaller the smaller the larger the film thickness of the hole transport layer. desirable.

Moreover, the height of the peeling edge part of the organic electroluminescent layer (PPV) formed after formation of the said hole transport layer was also evaluated.

As a result, in Examples 1-5 with respect to Comparative Examples 1-4, it was confirmed that the height of the peeling edge part of an organic EL layer is relatively small.

According to the present invention, when masking an application-free area on a substrate with a masking tape and applying a coating liquid made of a flowable material to form a thin film, an undesired increase in thickness of the thin film (coating film) around the tape is prevented from occurring. can do.

Claims (9)

As a masking tape for a board | substrate which has an adhesion layer in one surface of a base material, The contact angle of water in the other surface of a base material is less than 65 degrees, Masking tape for board | substrates whose contact angle of water in the side surface of an adhesion layer is less than 100 degrees. The method of claim 1, The masking tape for board | substrates characterized by having a separator in the to-be-adhered surface of an adhesion layer. The method of claim 1, The masking tape for board | substrates characterized by the base material consisting of a polyester film. The method of claim 1, The masking tape for board | substrates characterized by having a surface treatment layer on the other surface of a base material. The method of claim 1, The masking tape for board | substrates which has a surface treatment layer in the side surface of an adhesion layer. The method of claim 5, wherein A masking tape for a substrate, wherein the surface treatment layer is coated with a photocatalyst. The method according to any one of claims 1 to 6, A masking tape for a substrate, wherein the substrate is a glass substrate. The method according to any one of claims 1 to 6, A masking tape for substrates, wherein the substrate is a substrate for organic EL. The method according to any one of claims 1 to 6, A masking tape for a substrate, which is used for forming a thin film by a coating method for applying a fluid material from a nozzle toward a substrate.

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