JP3520775B2 - Low adhesion paint - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to the formation of a release liner for adhesive material, backside treatment of the single-sided tape, low formed from low adhesive coating material used in the oil-, antifouling treatment or the like of the electronic component
The present invention relates to a method for producing an adhesive coating film , and more particularly to a method for producing a low adhesive coating film for precision electronic devices which is required not to contain silicone.

[0002]

2. Description of the Related Art Generally, a pressure-sensitive adhesive tape is formed by forming a pressure-sensitive adhesive layer on a base material, which is distributed in a wound state and used while being unwound. In this adhesive tape, to prevent strong adhesion between the surface that carries the adhesive and the back surface that does not carry it, and to facilitate rewinding during use, make the adhesive surface of the adhesive tape Temporarily attached is a release liner for adhesive.

Conventionally, as a release liner for adhesives,
The mainstream is a film of polydimethylsiloxane. The reason is that 1) the force (peeling force) required to separate the adhesive liner for adhesive / adhesive material and the adhesive / adhesive surface that were once bonded together is low, and 2) the stability against aging is low. It is excellent, and 3) it can be manufactured at a relatively low cost.

Recently, however, the problem of silicone contamination in precision electronic devices has been highlighted, and silicone release liners tend to be shunned. That is, when the polydimethylsiloxane causes contamination inside the device by some route, the polydimethylsiloxane is decomposed by the electric energy generated during the operation of the electronic device and becomes a solid particle of silicon dioxide, which is the driving system of the electronic device. It is thought to be deposited in a subtle space and cause motion inhibition of the drive system and scratches. In particular, a hard disk device, which is a recording medium, is sensitive to this problem due to its high airtightness, the short distance between the recording head and the disk due to the high density, and the high speed rotation of the disk. Therefore, not only the materials of the components that directly compose electronic devices but also the indirect materials that come into contact with these components are required to be non-silicone in order to prevent migration contamination from the materials. Release liners are also required to be non-silicone.

There are non-fluorine-based and fluorine-based release agents for forming non-silicone release liners for adhesives and adhesives. Examples of the non-fluorine-based release agents are alkyl pendants and condensation waxes (adhesives). Handbook 163 pages-1
(See page 71) and the like are known. All of these are 2 to 10 N / for an acrylic pressure-sensitive adhesive having strong adhesiveness.
It is a medium peel force of about dm, and it is difficult to give a light peel force preferred in the market, that is, 0.2 to 2 N / dm.

On the other hand, a fluorine-containing acrylic polymer is known as a fluorine-based release agent. Depending on the design, this fluorinated acrylic polymer gives a peeling force of 2 to 4 N / dm, but it is still heavier than the peeling force desired in the market. Further, the fluorine-containing acrylic polymer has a problem that it has a strong tendency to stick-slip upon peeling.

As a fluorine-based release agent, a release agent mainly composed of perfluoropolyether is also known (Japanese Patent Laid-Open No. Hei 3 (1999) -311).
No. 258863). Although this release agent provides a sufficiently light release property, perfluoropolyether is extremely expensive and therefore is disadvantageous in terms of cost. Also, in the step of producing a release liner for adhesives from this release agent, the release agent is applied to the base material to cure the thin film, but at the time of curing, UV irradiation is performed in an inert gas. Is required, which is very complicated as compared with ordinary solvent coating. Also, the adhesiveness to the substrate is not sufficient. As a method for improving the adhesiveness to a substrate, it has been proposed to coat the substrate with a primer containing a special acrylic monomer that is copolymerizable with perfluoropolyether as a main component in advance (Japanese Patent Laid-Open No. 3-30083). 4075
No. 4, U.S. Pat. 4,567,073 and 4,
614, 667), the manufacturing process of the release liner for adhesive / bonding material becomes more complicated, and the cost is increased.

[0008]

SUMMARY OF THE INVENTION In order to solve the problems of the prior art as described above, the present invention can easily form a non-silicone type coating by simply applying a solution to a substrate and drying it, and
The coating shows sufficient adhesiveness to the substrate, but at least moderate peelability to the tacky adhesive layer such as acrylic pressure-sensitive adhesive having strong tackiness, preferably 2 N / dm
It has the following light peeling property, and the stability of the peeling force against aging is good. Furthermore, the tacky adhesive layer that has been once adhered to the coating and peeled has the same adhesive force as the initial one. The purpose is to

[0009]

Means for Solving the Problems The present inventor has found that a coating obtained by blending a specific fluorine-containing acrylic polymer and a fluorine-based oil in a specific ratio has a peeling force of the coating film to the adhesive layer. It has been found that the adhesive strength is small, the stick-slip tendency at the time of peeling is also reduced, the stability against aging, and the re-adhesiveness of the adhesive layer after being pasted with this coating are also good. Completed the invention.

That is, the present invention is a fluorine-containing acrylic resin having a crosslinkable reactive group, which is polymerized from a monomer composition containing an acrylic acid ester or a methacrylic acid ester having a perfluoroalkyl group having 6 to 16 carbon atoms as a main component. Polymer 99-33% by weight, and fluorinated oil 1-67% by weight
Was dissolved in a fluorinated solvent capable of dissolving the fluorine-containing acrylic polymer and the fluorine-based oil and at the same time, the resulting solution low adhesive coating obtained by adding a crosslinking agent or catalyst in
By coating the material on the film-forming substrate and allowing it to undergo a crosslinking reaction.
Low adhesion coating characterized by forming a low adhesion coating
A method for manufacturing a membrane is provided.

Further, there is provided a release liner for adhesive / bonding material in which a coating film of the low-adhesive coating material of the present invention is formed on one surface or both surfaces of the substrate, and an adhesive / adhesive layer is provided on one surface of the substrate. And a pressure-sensitive adhesive tape having a coating film of the low-adhesion paint of the present invention on the other surface.

According to the low-adhesive coating composition of the present invention, the fluorine-containing acrylic polymer and the fluorine-based oil are both fluorine-based in common with respect to the constituent elements, and the polymer is acrylic-based and fluorine-based. Oils have a moderate compatibility by balancing with the structural difference that they are generally ether-based or vinyl-based. Therefore, since the compatibility between the fluorinated acrylic polymer and the fluorinated oil is too poor, the fluorinated acrylic polymer and the fluorinated oil are strongly phase-separated and a uniform coating film cannot be formed, or conversely The solubility is too good to form a coating film in which the fluorinated acrylic polymer and the fluorinated oil are completely integrated. In the low-adhesive coating material of the present invention, the fluorine-containing acrylic polymer is uniformly plasticized (softened) by the fluorine-based oil in the coating film, and at the same time, a part of the fluorine-based oil seeps out to the coating film surface. It has the property of (bleeding).

It is generally known that, as the surface morphology (morphology) of the fluorinated acrylic polymer, it is preferable that the perfluoroalkyl group is oriented on the surface in order to reduce the peeling force. The coating formed from the low-adhesive paint of the above plasticizes (softens) as described above.
Since the molecules are easily moved, it is easy to take such a surface morphology. Further, the bleeding fluorine-based oil promotes the generation of such surface morphology, and after such surface morphology is generated, the bleeding fluorine-based oil fixes and stabilizes the morphology. Therefore, the coating film formed from the low-adhesive coating material of the present invention exhibits light releasability with respect to the adhesive layer.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The low-adhesive coating composition of the present invention comprises a specific fluorine-containing acrylic polymer and a fluorine-based oil.

This fluorinated acrylic polymer comprises a monomer composition containing a perfluoroalkyl group-containing acrylic acid ester or a perfluoroalkyl group-containing methacrylic acid ester (hereinafter referred to as a fluorine-based long-chain alkyl acrylic monomer) as a main component. It is a polymer obtained by polymerization and has a main chain formed by acrylic polymerization.

The fluorinated long-chain alkyl acrylic monomer is an acrylic acid ester and a methacrylic acid ester having a perfluoroalkyl group represented by the following formulas (1) and (2).

[0018]

Embedded image Rf—X—OCOCH═CH ₂ (1) Rf—X—OCOC (CH ₃ ) ═CH ₂ (2) (In the formulas (1) and (2), Rf is a perfluoroalkyl group. , X is a spacer group.)

Here, the carbon number of the perfluoroalkyl group of Rf is 6 to 16, and the carbon number is more preferably 8 to 12 in order to achieve a light peeling property of 2 N / dm or less. When the carbon number is less than 6, the peeling performance of the paint cannot be sufficiently obtained, and when the carbon number exceeds 16, the acquisition cost of the monomer itself is greatly increased, and a polymer having properties commensurate with that is obtained. This is because it is hard to be caught.

Specific examples of the perfluoroalkyl group of Rf include a linear perfluoroalkyl group of the formula (3),
As shown in Formula (4), a perfluoroalkyl group in which one F atom of an alpha carbon atom is substituted with an H atom, a branched perfluoroalkyl group as in Formula (5), and the like can be given.

[0021]

Embedded image CF ₃ (CF ₂ ) _n − (3) HCF ₂ (CF ₂ ) _n − (4) (CF ₃ ) ₂ CF (CF ₂ ) _m − (5) (wherein n is 5 to 15) , And m is an integer of 3 to 12.)

Further, in the formulas (1) and (2), the spacer group of X is not particularly limited, and a spacer group used in commonly available monomers can be used. For example, a methine group or an ethylene group of the formula (6), a hydroxypropyl group of the formula (7), or an N- of the formula (8).
Examples thereof include an alkylsulfamide group.

[0023]

## STR3 ## _{- (CH 2) p - (} 6) -CH 2 CH (OH) CH 2 - (7) -SO 2 N (C q H 2q + 1) -CH 2 CH 2 - (8) ( Formula In (6), p is an integer of 1 or 2 and is represented by the formula (8)
In the above, q is an integer of 2, 3 or 4. )

In the present invention, the proportion of the fluorine-containing long-chain alkyl acrylic monomer in the monomer composition is preferably as high as possible, preferably 75% by weight or more, and more preferably 90% by weight or more. From the standpoint of peeling performance,
All the constituent monomers of the monomer composition may be fluorinated long-chain acrylic monomers.

The monomer composition may contain other monomers in addition to the fluorine-containing long-chain alkyl acrylic monomer. Thereby, the adhesion of the coating film to the substrate such as PET is improved, the cohesive force of the fluorinated acrylic polymer is increased, or the polarity is adjusted (solvent solubility, SP
The value can be adjusted, the compatibility with the fluorinated oil can be adjusted). For example, a homopolymer of a fluorinated long-chain alkyl acrylic monomer having 10 or more carbon atoms is difficult to dissolve even in a fluorinated solvent, but its solubility can be improved by copolymerizing another monomer.

The monomer to be copolymerized with the fluorinated long-chain alkyl acrylic monomer is not particularly limited, and general-purpose monomers such as methacrylic acid and alkyl esters of acrylic acid, styrene, vinyl acetate and acrylonitrile may be used. From the viewpoint of peeling performance, it is preferable to use another fluorine-based monomer, for example, a fluorine-containing short-chain alkyl acrylic monomer having 1 to 5 carbon atoms.

In the present invention, as a polymerization method for obtaining the fluorine-containing acrylic polymer, the above-mentioned monomer composition may be polymerized by a known radical polymerization method. In this case, as the polymerization mode, known emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization or the like can be used. When the majority of the fluorine-containing long-chain alkyl acrylic monomer is contained in the monomer composition, A in the presence of a fluorine-based solvent is used.
A method of solution polymerization using an initiator such as IBN can be used. Alternatively, it is also effective to use a general-purpose solvent (for example, ethyl acetate) in a small amount to bring the monomer into a high-concentration suspension-dispersion state and perform polymerization. When a monomer other than the fluorinated long-chain alkyl acrylic monomer is copolymerized, it is also possible to carry out solution polymerization in a general-purpose solvent (eg ethyl acetate).

Further, the fluorine-containing acrylic polymer does not have to be particularly crosslinked, but by crosslinking it becomes possible to add a larger amount of fluorine oil to the low adhesive coating of the present invention. It is possible to reduce the peeling force with respect to the adhesive layer. In addition, since the cohesive force of the coating can be improved by crosslinking, it is possible to improve the adhesiveness of the coating to the base material.

The cross-linking method may be a method in which a reactive group such as a hydroxyl group, a carboxyl group, a glycidyl group or an alkoxysilane group is previously introduced into a fluorine-containing acrylic polymer, and a reactive cross-linking agent is used to bond the group. , A method in which two reactive groups having reactivity with each other are introduced into the fluorine-containing acrylic polymer (on separate molecules or on one molecule at the same time), and the reaction is promoted by addition of a catalyst to bond them, or A method is used in which a self-crosslinking reactive group is introduced, and the reaction is promoted by adding a catalyst to bond.

Here, as a method of introducing a reactive group or a polar group into the fluorine-containing acrylic polymer, HEMA (hydroxyethyl methacrylate), HEA (hydroxyethyl acrylate), methacrylic acid, acrylic acid, GMA
It is simple and effective to copolymerize a reactive group-containing monomer represented by (glycidyl methacrylate), isocyanatoethyl methacrylate, alkoxysilane-containing acrylate or alkoxysilane-containing methacrylate with a fluorine-based long-chain alkyl acrylic monomer.

Further, when the fluorine-containing long-chain acrylic monomer is the only constituent monomer of the monomer composition, a method of introducing a reactive group into the polymer is to add a functional group such as a hydroxypropyl group to the spacer X. An appropriate amount of the fluorine-based monomer having the spacer having the above may be introduced.

On the other hand, the fluorinated oil used in the present invention is a fluorinated compound which has virtually no boiling point at atmospheric pressure and has a vapor pressure of 10 ^-2 Torr or less at room temperature and is liquid at room temperature. Or those having a pour point of not higher than room temperature.

Examples of the fluorinated oil include perfluoropolyether oil and the following formula (9).

[0034]

## STR00004 ##-(CF ₂ CFCl) _n- (9) (Daikin Industries, Ltd .: Daifloyl), a trifluorochloroethylene low polymer, a fluorine-based surfactant, a perfluoroalkyl phosphate, etc. are used. be able to. Particularly preferred among these are perfluoropolyether oils.

The perfluoropolyether oil has no functional group as shown in the following formulas (10), (11), (12) and (13), or the following formula (14),
Those having a functional group as shown in (15) are commercially available, and both can be used.

[0036]

Embedded image F (CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₃ (10) (Daikin Industries, Ltd .: Demnum) C ₃ F ₇ O (CF (CF ₃ ) CF ₂ O) _n CF ₂ CF ₃ (11) (EIDupont de Nemours and Company , Inc.: Krytox GPL, Krytox 143, Kryto x VPF) CF 3 - (OCF (CF 3) CF 2) n - (OCF 2) m -OCF 3 (12) (Ausimont Corporation _{Ltd.: Fomblin Y, GALDEN) CF 3} - (OCF 2 CF 2) n - (OCF 2) m -OCF 3 (13) (Ausimont Corporation: Fomblin Z, Fomblin M) X -CF 2 - (OCF 2 CF 2 _{) n - (OCF 2) m} -OCF 2 -X (14) (Ausimont Corporation: Fomblin Z derivatives; wherein, X is _{COOH, CH 2 OH, CH 2} OCH 2 CH (OH) CH 2 OH, CH 2 _{(OCH 2 CH 2) n -OH} , showing the COO R, _{etc.) CF 3 -. (OCF (} CF 3) CF 2) n - (OC _{2) m -Y (15) (} Ausimont Corporation: GALDEN MF series; wherein, Y represents a carboxylic acid, phosphoric acid esters, alcohols, amidosilane, laden group a functional group such as an alkyl amide).

In the low-adhesive coating composition of the present invention, it is preferable that the fluorinated oil is adjusted so that it bleeds properly from the coating film. Excessive bleeding will adversely affect the re-adhesiveness of the tacky adhesive layer once it has been attached to this coating.

The bleeding can be adjusted by appropriately selecting the type and molecular weight of the perfluoropolyether used as the fluorinated oil. That is, among the perfluoropolyethers, those having a functional group have less bleeding than those having no functional group, and those having a lower molecular weight have less bleeding than those having a higher molecular weight. However, when a perfluoropolyether having a functional group is used in the presence of a crosslinking agent, it is necessary to take care so that the functional group does not react with the crosslinking agent and the perfluoropolyether is resinified. Therefore, it is preferable to design the cross-linking agent so that it reacts preferentially with the functional groups of the fluorinated acrylic polymer rather than with the functional groups of the perfluoropolyether.

In the low-adhesive coating composition of the present invention, the mixing ratio of the fluorine-containing acrylic polymer and the fluorine-based oil is 99 to 33% by weight of the fluorine-containing acrylic polymer and the fluorine-based oil 1 to 67.
It is preferable that the content of the fluorine-containing acrylic polymer is 95 to 67% by weight, and the content of the fluorine-based oil is 5 to 33% by weight. Although the peeling force can be made lighter by increasing the amount of the fluorinated oil, the re-adhesion force tends to decrease, and the fluorinated oil is more expensive than the fluorinated acrylic polymer. Blending a large amount of the system oil increases the production cost of the coating material of the present invention.

The low-adhesive coating material of the present invention may contain a solvent in order to adjust the proper viscosity and the film thickness during coating. As this solvent, those capable of simultaneously dissolving the fluorinated acrylic polymer and the fluorinated oil are preferable, and for example, a fluorinated solvent is preferable. Specific examples of the fluorine-based solvent include perfluoroalkanes (3M, PF series), low molecular weight perfluoropolyether (Ausimont, GALDEN), trifluorobenzene, hexafluoroxylene, perfluoroalkyltetrahydrofuran, and the like. These mixtures etc. are illustrated. Further, general-purpose solvents other than fluorine-based, a fluorine-containing acrylic polymer is a copolymer soluble in a general-purpose solvent,
Fluorine-based oil can also be used when it is soluble in a general-purpose solvent such as Daifloyl manufactured by Daikin Industries, Ltd.

Further, the low-adhesive coating material of the present invention may be blended with an appropriate amount of a filler for coloring or roughening the surface as long as the peelability is not impaired. As the filler, general inorganic fillers, carbon particles, pigments ,
It is possible to formulate a full Tsu of carbon or the like.

The concentration of the low-adhesive coating material of the present invention is preferably such that a dry film having a thickness of 10 nm to 10 μm can be formed on a substrate. Dry film thickness is 10
If it is less than nm, the releasability tends to be poor. On the contrary, 1
If it exceeds 0 μm, the cost tends to be high, and the adhesiveness to the substrate tends to be low. The thickness of the dry film is from 10 nm
The coating concentration of 10 μm can be determined from the wet coating weight of the coater used and the dry weight of the desired coating.

The low-adhesive coating composition of the present invention comprises a release liner for tacky adhesive tape, a release treatment for the back surface of a one-sided tacky adhesive tape,
It can be used for antifouling treatment of various electric / electronic components and substrates such as glass epoxy substrates, oil barrier treatment of precision machine parts, water / oil repellent treatment, etc. In particular, it is useful as a paint when forming a film for precision anti-fouling treatment or the like on precision electronic devices that are required not to contain silicone.

More specifically, for example, in the case of forming a release liner for tacky-adhesive material, the low-adhesive coating material of the present invention may be coated on a substrate and then dried to form a film on the surface of the substrate. The single-sided pressure-sensitive adhesive tape which has been subjected to the back surface peeling treatment has a low adhesiveness of the present invention on the surface of the base material on the opposite side of the pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer on one surface of the base material. The coating may be formed by coating with a water-soluble paint and drying.

Here, as the base material, polyester film, polyolefin film, polyamide film, polyimide film, polyolefin laminated paper, papers (parchment paper, glassine paper,
Sealing coated paper), metal vapor deposition film, metal foil and the like are suitable. As a coating device, a general coater such as a roll coater, a knife coater, a pipe coater or a gravure coater can be used.

When the coating film of the low-adhesive coating material of the present invention is formed for the purpose of antifouling treatment, oil barrier treatment, water / oil repellent treatment, etc. on various electric / electronic parts, substrates, precision machine parts and the like. In addition to the above-mentioned coater, it may be coated by a method such as dipping, brush coating, or spraying.

Drying conditions after coating the low-adhesive coating material of the present invention on a predetermined substrate are not particularly required as long as a film can be formed. When the formation of the film is hindered by the dew condensation, it may be dried in an oven at about 60 to 120 ° C. When the crosslinking reaction is performed, it may be heat-treated at the temperature of the reaction conditions after drying.

[0048]

EXAMPLES The present invention will be specifically described below based on examples. In addition, Example 8 contains PTFE fine particles.
It is a reference example using a fluorinated oil.

Examples 1 to 4 (1) Synthesis of Fluorine-Containing Acrylic Polymer A Perfluorooctylethyl methacrylate (CH ₂ ═C) was added to a 1 liter flask equipped with a stirrer and a reflux tube.
200 g of (CH ₃ ) COOCH ₂ CH ₂ C ₈ F ₁₇ )
And 50 g of ethyl acetate are charged, and 80
The temperature was raised to ° C. Next, 0.6 g of azobisisobutyl nitrile (AIBN) was dissolved in 6 g of MEK, and this was added to the reaction system to initiate polymerization. Polymerization was separated into two layers, an upper layer and a lower layer, and proceeded in a semi-suspended state. After 4 hours, the reaction was stopped, and after cooling, the mixture was left standing overnight. Phase separation was performed into 245 g of a waxy polymer layer (lower layer) and 5 g of a solvent layer (upper layer). The polymer layer was taken out of the flask, pulverized, and then ethyl acetate was removed to obtain a powdery fluorine-containing acrylic polymer A.

(2) Preparation of low-adhesive coating composition 1 g of the fluorine-containing acrylic polymer A obtained in (1) was mixed with FR thinner (a mixture of perfluoro-2-butyltetrahydrofuran, metaxylenehexafluoride and perfluoroalkane; Shin-Etsu). 90 g (made by Kagaku Kogyo Co., Ltd.). In this, perfluoropolyether oil (Fomblin Z derivative DIAC4000: carboxylic acid modified type at both ends; molecular weight 4000) manufactured by Ausimont Co., Ltd. as a fluorinated oil was dissolved by changing it from 0.1 g to 1.5 g. It was

(3) Preparation of release liner The coating material obtained in (2) was applied to a corona-treated polyethylene terephthalate film having a thickness of 50 μm by a wire rod of # 5 at about 8 g / m ^{2 and} heated at 110 ° C. for 5 minutes. A release liner was obtained by drying.

(4) An acrylic double-sided adhesive tape (T-3500 manufactured by Sony Chemical Co., Ltd.) was applied to the coating surface of the release liner obtained in Evaluation (3).
Were pasted together and passed through a silicone roll at a linear pressure of 2.4 kg / cm for pressure bonding. After that, it was cut into a size of 5 cm × 20 cm, placed in an oven at 70 ° C. for 24 hours with a load of 2.5 kg, and aged. It was returned to room temperature and the peeling force (converted to dm width) was measured in a T-type peeling mode at a speed of 300 cm / min with a Tensilon type tensile tester.

Immediately after the peeling, a new polyethylene terephthalate film having a thickness of 50 μm was attached to the peeled surface of the adhesive tape, and the mixture was pressed through a silicone roll at a linear pressure of 2.4 kg / cm. This was cut into a width of 2 cm, the peeling force was measured in a T-type peeling mode at a speed of 300 cm / min with a Tensilon type tensile tester, and this was taken as the readhesion force (converted to dm width).

On the other hand, an adhesive tape (T-3500 manufactured by Sony Chemical Co., Ltd.) after being adhered to a silicone-based release paper
The re-adhesion strength to the polyethylene terephthalate film was determined in the same manner as above. As a result, the re-adhesion force is 21.
It was 6 N / dm. Then, the ratio of the re-adhesion force of the pressure-sensitive adhesive tape after being bonded to the above-mentioned release liner to this value was obtained.

30 ml of the coating material obtained in (2) was poured into an aluminum cup and evaporated to dryness in an oven at 110 ° C.
From the appearance and feel of the film, the fluorinated acrylic polymer A
And the degree of bleeding were investigated with fluorinated oil (perfluoropolyether oil).

The results are shown in Table 1. From Table 1, the peeling force of Examples 1 to 4 was 2 N / dm or less, and their readhesion force was also good. The appearance of the dry film was a transparent and flexible film, and the compatibility between the fluorinated acrylic polymer A and the fluorinated oil was fairly good. Then, only slight bleeding was observed on the surface of the fluorinated oil.

Comparative Example 1 Using the same fluoropolymer A as in Examples 1 to 4, a release liner was prepared and evaluated in exactly the same manner as in Example 1 without mixing the fluorinated oil. The results are shown in Table 1.

The peeling force after aging was 2.06 N, which was slightly inferior to obtain a light peeling force of 2 N or less. The peeling mode had a strong tendency to stick-slip.

Comparative Example 2 Using the same fluorine-containing acrylic polymer A as in the above-mentioned example, the amount of fluorine-based oil was adjusted to 3 of the fluorine-containing acrylic polymer.
A release liner was prepared and evaluated in exactly the same manner as in the example except that the amount was doubled. The results are shown in Table 1.

The surface of the coating film of the obtained release liner was sticky, and the peeling force after aging was sufficiently light peeling, but the re-adhesion force was obviously poor and the peeling to the adhesive surface of the pressure-sensitive adhesive tape was carried out. The transfer stain of the liner coating was large.
The shape of this dry film was a highly viscous fluid liquid. It can be seen that the polymer causes cohesive failure when the amount of the fluorinated oil is too large.

[0061]

[Table 1] Examples Comparative Examples 1 2 3 4 1 2・ Fluorine-containing acrylic polymer A (g) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 ・ Fluorine oil (g) 0.10 0.25 0.62 1.5 None 3.00 ・ Peeling force after aging (N / dm) 1.27 0.88 0.63 1.26 2.06 0.49 ・ Re-adhesion force (N / dm) 25.3 22.8 17.2 13.7 27.7 7.30 ・ Re-adhesion force ratio to silicone release paper (%) 117 106 79.6 63.4 128 33.8 ・ Appearance of dry film * 1 A A A B C D E bleeding * 2 a a a b c- Table 1 Note * 1: A ... transparent and a little flexible B ... transparent and flexible C ... transparent and very flexible D ... transparent and brittle and hard E ... transparent and sticky high Viscous flowing liquid (hardness: E <A <B <C <D) * 2: a ... very small b ... small c ... none

Examples 5-8 1 g of the same fluorinated acrylic polymer A as used in the above examples was dissolved in 90 g of FR thinner and then Table 2
As shown in, 0.25 of fluorine-based oil having no functional group
g was added to it and dissolved to obtain a coating.

Using the obtained paint, the peeling force and the re-adhesion force were measured and the appearance and bleeding of the dried film were examined in the same manner as in the above-mentioned examples. The results are shown in Table 2.

In Examples 5, 7 and 8, regarding the compatibility between the fluorinated acrylic polymer A and the fluorinated oil, the coatings were all slightly flexible films and the bleeding was small. Moreover, both the peeling force and the re-adhesion force were good. In Example 6 using a fluorine-based oil having a high molecular weight, the coating was not completely transparent, the compatibility was a little low, and the bleeding was a little large, but both the peeling force and the re-adhesion force were good. The semi-transparency of the film of Example 8 was P.
This is due to the addition of TFE fine powder.

[0065]

[Table 2]
Example 5 6 7 8 Fluorine-based oil Krytox Krytox DYFLOIL DEMNUM 1506 * 1 1525 * 1 # 20 * 2 Grease L-65 * 3 ・ Compounding ratio of polymer A and fluorine-based oil 1 / 0.25 1 / 0.25 1 / 0.25 1 / 0.25 ・ Peeling force after aging (N / dm) 1.4 1.1 1.7 1.1 ・ Re-adhesion force (N / dm) 30.6 29.4 29.4 29.4 ・ Appearance of dry coating * 4 A A '' A A'-Bleeding * 5 a b a a Table 2 Note * 1: Made by EIDupont de Nemours and Company * 2: Made by Daikin Kogyo * 3: Made by Daikin Kogyo, containing 35% by weight of PTFE fine powder * 4: A ... Transparent and slightly flexible A '... Semi-transparent and slightly flexible A''... Semi-transparent and slightly flexible (Flexibility A>A'> A '') * 5: a ... Small b ... Slightly large

Examples 9 to 11 In a 1-liter flask equipped with a stirrer and a reflux tube, perfluorooctylethyl methacrylate (CH ₂ = C) was added.
(CH ₃ ) COOCH ₂ CH ₂ C ₈ F ₁₇ ) and HEMA (hydroxyethyl methacrylate) were added at a ratio shown in Table 3 in a total amount of 100 g, and then 42 g of ethyl acetate was added, followed by the same method as in Example 1. Polymerization was carried out to obtain fluorinated acrylic polymers B, C and D. Next, 1 g of these was dissolved in 90 g of FR thinner, and then 0.25 g of fluorine-based oil (Fomblin Z derivative DIAC4000 manufactured by Ausimont) was further dissolved to obtain a coating material.

This coating material was evaluated in the same manner as in Example 1. The results are shown in Table 3. As shown in Table 3, the compatibility of the fluorine-containing acrylic polymers B, C, and D with the fluorine-based oil was all relatively good, and the bleeding was very slight. The peelability tended to be inferior as HEMA increased.

Example 12 A fluorine-containing acrylic polymer E was obtained in the same manner as in Example 11 except that 2 g of γ-methacryloxypropyltrimethoxysilane was used instead of HEMA. Then 1g of this
Was dissolved in 90 g of FR thinner, and 0.2 of a fluorinated oil (Ausimont, Fomblin Z derivative DIAC4000) was added.
5 g was blended and dissolved. 0.02 g of perfluorooctyl phosphate ester was added as a catalyst to obtain a coating material of this example.

This paint was evaluated in the same manner as in Example 1. The results are shown in Table 3.

The compatibility between the polymer E and the fluorinated oil was relatively good, and the bleeding was very slight. Further, the peelability was good.

[0071]

[Table 3] Example 9 10 11 12・ Fluorine-containing acrylic polymer B C D E ・ FMA * 1 to copolymer monomer ratio 98.7 / 1.3 * 2 96.0 / 4.0 * 2 93.9 / 6.1 * 2 98.0 / 2.0 * 3 ・ Polymer Mixing ratio of fluorinated oil with 1 / 0.25 1 / 0.25 1 / 0.25 1 / 0.25 ・ Peeling force after aging (N / dm) 1.6 4.9 8.6 1.0 ・ Re-adhesion force (N / dm) 22.5 26.5 29.4 29.4 ・ Drying Appearance of coating * 4 A A A A bleeding * 5 a a a a Table 3 Note * 1: FMA (perfluorooctylethyl methacrylate) * 2: HEMA (hydroxyethyl methacrylate) * 3: ASMA (γ-methacryloxypropyl) (Trimethoxysilane) * 4: A ... Transparent and slightly flexible * 5: a ... Very small

Comparative Examples 3 to 6 Fluorine-containing acrylic polymers B of Examples 9 to 12 above
1 g of E was dissolved in 90 g of FR thinner to obtain a coating material containing no fluorine-based oil. The obtained coating material was evaluated in the same manner as in Example 1. The results are shown in Table 4.

The peeling properties of the coating films of the paints of Comparative Examples 3 to 6 were heavier than those of the corresponding Examples 9 to 12 to which the fluorinated oil was added.

[0074]

[0075]

[Table 4] Comparative Example 3 4 5 6・ Fluorine-containing acrylic polymer B C D E ・ Ratio of FMA * 1 and copolymerization monomer 98.7 / 1.3 * 2 96.0 / 4.0 * 2 93.9 / 6.1 * 2 98.0 / 2.0 * 3 ・ Polymer Mixing ratio of fluorinated oil and fluorinated oil ← ← ← ・ Peeling force after aging (N / dm) 2.2 6.1 9.0 2.1 ・ Re-adhesion force (N / dm) 28.4 29.4 30.6 ＞ 30.6 ・ Appearance of dry film * 4 F F F F Table 4 Note * 1: FMA (perfluorooctylethylmethacrylate) * 2: HEMA (hydroxyethylmethacrylate) * 3: ASMA (γ-methacryloxypropyltrimethoxysilane) * 4: F: hard resin Condition

Examples 13 to 14 In a 1 liter flask equipped with a stirrer and a reflux tube,
(Perfluoro-7-methyl-octyl) ethyl methacrylate _{(CH 2 = C (CH 3} ) COOCH 2 CH 2 (C
25 g of F ₂ ) ₆ CF (CF ₃ ) ₂ ) (M-3820 from Daikin Fine Chemical Co., Ltd.) and 15 g of ethyl acetate were charged, and the temperature was raised to 80 ° C. under a nitrogen gas atmosphere. Next 0.0
1 g of 8 g of azobisisobutyronitrile (AIBN)
Dissolved in MEK and added to the reaction system to initiate polymerization. It solidified after 7 hours, so 40 mL of ethyl acetate was added. The reaction mixture separated into two layers. The lower layer (polymer layer) is taken out and dried to give a fluorine-containing acrylic polymer F.
Got

On the other hand, as the acrylic monomer, 2- (perfluoro-9-methyldecyl) ethyl methacrylate (CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₈ C
F (CF ₃ ) ₂ ) (Daikin Fine Chemical Co., M-4
Fluorine-containing acrylic polymer G was obtained in exactly the same manner as described above except that 020) was used.

1 g of each of these polymers F and G was dissolved in 90 g of FR thinner, and 0.33 g of perfluoropolyether (Fomblin M60: average molecular weight 12,500) manufactured by Ausimont Co. was used as a fluorine-based oil. In addition, a paint was prepared and the obtained paint was evaluated in the same manner as in Example 1. The results are shown in Table 5.

The coating film of this example had a good peeling force.
Further, the compatibility between the fluorinated acrylic polymers F and G and the fluorinated oil was slightly low, and the bleeding was also slightly high. However, its readhesion was good.

Comparative Examples 7 to 8 Paints were prepared and evaluated in the same manner as in Examples 13 to 14 except that the fluorine oil was not added. The results are shown in Table 5.

The peeling forces of the coating films of these Comparative Examples 7 to 8 were heavier than those of the corresponding Comparative Examples 13 to 14 containing the fluorinated oil. Further, in Comparative Example 8, the peeling mode had a strong stick-slip tendency.

[0082]

[Table 5] Examples Comparative Example 13 14 78 ・ Fluorine-containing acrylic polymer F G F G ・ Blending ratio of polymer and fluorine oil 1 / 0.33 1 / 0.33 No addition ← ・ Peeling force after aging (N / dm) 2.9 1.1 5.1 2.0 * 1 ・ Re-adhesion force (N / dm) 30.4 28.9 27.4 28.4 ・ Appearance of dry film * 2 A '' A '' − − · Bleeding * 3 dd − − Table 5 Note * 1: Stick-slip Strong tendency * 2: A '' ... Semi-transparent and slightly flexible * 3: d ... Moderately large

[0083]

EFFECTS OF THE INVENTION According to the low-adhesive coating composition of the present invention, a non-silicone type coating can be easily formed simply by coating the coating on a substrate and drying it, and the coating can be applied to the substrate. Although it exhibits sufficient adhesiveness, it exhibits a moderate to light peeling force to a tacky adhesive layer such as an acrylic pressure-sensitive adhesive. Further, the aging stability of the peeling force becomes good, and further, the adhesive layer after being once adhered to the coating film of the present invention exhibits good re-adhesion property.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09D 4/00-201/10 C09K 3/00 C09J ⁷ /00-7/04

Claims (4)

(57) [Claims] 1. A fluorine-containing acrylic polymer 99-having a crosslinkable reactive group, which is polymerized from a monomer composition containing an acrylic acid ester or a methacrylic acid ester having a perfluoroalkyl group having 6 to 16 carbon atoms as a main component. 33 wt%, and fluorine-based oil 1 to 67% by weight, dissolved in a fluorinated solvent capable of dissolving the fluorine-containing acrylic polymer and the fluorine-based oil and at the same time, the resulting solution a crosslinking agent or catalyst The low-adhesive paint obtained by adding
A low-adhesion coating film can be obtained by applying it on top and causing a crosslinking reaction.
A method for producing a low-adhesion coating film , which comprises forming . 2. The fluorine-containing acrylic polymer has 8 to 8 carbon atoms.
The production method according to claim 1, which is a polymer of a monomer composition containing 75% by weight or more of acrylic acid ester or methacrylic acid ester having 12 perfluoroalkyl groups. 3. The fluorine-containing acrylic polymer has 8 to 8 carbon atoms.
The production method according to claim 2, which is a polymer of a monomer composition containing 90% by weight or more of acrylic acid ester or methacrylic acid ester having 12 perfluoroalkyl groups. 4. The method according to claim 1, wherein the crosslinkable reactive group is a hydroxyl group, a carboxyl group, a glycidyl group or an alkoxysilane group.