JP2006272690A - Antistaining protection film, antistaining adhesive protection film and outdoor marking film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a antistaining protection film with an antistaining layer formed on a plastic film base, having excellent adhesion properties between the plastic film base and the antistaining layer, and not undergoing deterioration in transparency and antistaining function, even if the film is exposed to the outdoor for a long time, and an antistaining adhesive protection film and an outdoor marking film using the antistaining adhesive protection film. <P>SOLUTION: In this antistaining protection film, the antistaining layer is a layer composed of a crosslinked product of an oil/fat-modified alkyd resin, a fatty acid-modified alkyd resin or a silicone-modified alkyd resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an antifouling protective film, an antifouling adhesive protective film, and an outdoor marking film.
In more detail, the present invention has an antifouling layer formed on a plastic film substrate, and has excellent adhesion to the plastic film substrate of the antifouling layer and is transparent even when subjected to long-term outdoor exposure. The present invention relates to an antifouling protective film, an antifouling adhesive protective film, and an outdoor marking film using the same.

  Marking film has better design uniformity, mass productivity, and ease of construction compared to painting, and is often used outdoors as a signboard or as a decoration or display material for automobiles. When exposed, the wind and dust will cause dust and dirt to adhere and damage the appearance. Therefore, it is often performed to overlaminate an antifouling protective film for the purpose of preventing and protecting the surface dirt.

  This antifouling protective film is applied not only to marking films but also to items that require prevention and protection of surface contamination, and is formed by forming an antifouling layer on a plastic film substrate. is there.

As the antifouling layer, many materials composed of hydrophilic or hydrophobic materials are designed. For example, a silane compound having a hydrolyzable group such as an alkoxy group and an alkyl group, an alkoxy group, a perfluoroalkyl group, etc. For example, Patent Documents 1 and 2), photocatalysts such as titanium oxide (for example, see Patent Document 3), and the like have been proposed.
However, when a silane compound is used, the adhesion to the substrate is not sufficient, and when a photocatalyst such as titanium oxide is used, ultraviolet rays are required to exert the antifouling function. Furthermore, it is not suitable for applications that require transparency.

JP 2004-59953 A JP 2004-246239 A JP 2003-306563 A

  The present invention provides an antifouling protective film that has excellent adhesion to the plastic film substrate of the antifouling layer and does not deteriorate its transparency and antifouling function even under long-term outdoor exposure under such circumstances. And an antifouling adhesive protective film and an outdoor marking film using the same.

  As a result of intensive studies to achieve the above object, the present inventors made the antifouling layer a layer composed of a cross-linked product of an oil-modified alkyd resin, a fatty acid-modified alkyd resin, or a silicone-modified alkyd resin. We found that the objective could be achieved. The present invention has been completed based on such findings.

That is, the present invention
(1) An antifouling protective film in which an antifouling layer comprising a cross-linked product of an oil- and fat-modified alkyd resin, a fatty acid-modified alkyd resin or a silicone-modified alkyd resin is formed on a plastic film substrate,
(2) The antifouling protective film of (1) above, wherein the antifouling layer has a thickness of 0.01 to 10 μm,
(3) A cross-linked product of an oil- and fat-modified alkyd resin, a fatty acid-modified alkyd resin or a silicone-modified alkyd resin is crosslinked using an amino resin, a urethane resin, an epoxy resin, an acrylic resin or a phenol resin as a crosslinking agent. The antifouling protective film according to any one of (1) to (2) above,
(4) In the antifouling protective film according to any one of the above (1) to (3), an antifouling adhesive protection comprising a pressure-sensitive adhesive layer formed on the surface of the plastic film substrate on which the antifouling layer is not formed. Film, and (5) an outdoor marking film in which the antifouling adhesive protective film of (4) above is affixed to the surface,
Is to provide.

  The antifouling protective film and antifouling adhesive protective film of the present invention and the outdoor marking film using the same are excellent in adhesion to the plastic film substrate of the antifouling layer and exhibit an antifouling function immediately after use. Moreover, the transparency and antifouling function do not deteriorate even when subjected to long-term outdoor exposure.

The plastic film substrate used in the antifouling protective film of the present invention is not particularly limited and can be appropriately selected depending on the purpose of use and the situation, but in consideration of application to an outdoor marking film or the like, it is transparent. And those having weather resistance are preferable, and include polyolefin films such as polyethylene films and polypropylene films, polyester films such as polyethylene terephthalate (PET) films and polyethylene naphthalate films, polystyrene films, polycarbonate films, and acrylic resin films. it can. Among these plastic film substrates, PET films and acrylic resin films are preferred because they are excellent not only in transparency and weather resistance but also in adhesion to the antifouling layer.
Although the thickness of a plastic film base material can also be suitably selected according to a use purpose or a condition, Usually, the range of 10-500 micrometers is preferable, and it is especially preferable that it is the range of 15-300 micrometers.

The antifouling layer in the antifouling protective film of the present invention is a layer comprising a cross-linked product of an oil- and fat-modified alkyd resin, a fatty acid-modified alkyd resin or a silicone-modified alkyd resin (sometimes referred to as “modified alkyd resin” in the following description). It is.
The oil-modified alkyd resin, the fatty acid-modified alkyd resin, and the silicone-modified alkyd resin are resins obtained by a condensation reaction of a polyhydric alcohol, a polybasic acid, and a corresponding modifier.

  Examples of the polyhydric alcohol used as a raw material for the alkyd resin include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, and neopentyl glycol, glycerin, trimethylolethane, Examples thereof include trihydric alcohols such as trimethylolpropane, and polyhydric alcohols such as diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, and sorbit. These may be used singly or in combination of two or more.

  Examples of the polybasic acid include aromatic polybasic acids such as phthalic anhydride, terephthalic acid, isophthalic acid, and trimetic anhydride, aliphatic saturated polybasic acids such as succinic acid, adipic acid, and sebacic acid, maleic acid, and maleic anhydride. Diels Alder such as acid, fumaric acid, itaconic acid, aliphatic unsaturated polybasic acid such as citraconic anhydride, cyclopentadiene-maleic anhydride adduct, terpene-maleic anhydride adduct, rosin-maleic anhydride adduct Examples thereof include polybasic acids by reaction. These may be used singly or in combination of two or more.

As the modifier, in the case of oil-modified alkyd resin and fatty acid-modified alkyd resin, for example, octyl acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid, dehydrated ricinolein Acid, coconut oil, linseed oil, drill oil, castor oil, dehydrated castor oil, soybean oil, safflower oil, and fatty acids thereof can be used.
These may be used individually by 1 type, and may be used in combination of 2 or more types.

  In the case of a silicone-modified alkyd resin, as the modifier, for example, a compound having an alkoxysilyl group or a silanol group, specifically, an organopolysiloxane mainly composed of dimethylpolysiloxane can be used. The moiety may be substituted with a phenyl group, an ethyl group, an isopropyl group, a hexyl group, a cyclohexyl group, a hydroxyl group, a vinyl group, or the like.

In order to obtain an antifouling layer excellent in adhesion and durability to the substrate, which is the effect of the present invention, the modification rate of the modified alkyd resin is 5 in the case of the oil-modified alkyd resin and the fatty acid-modified alkyd resin. The range of ˜60% by mass is preferable, and in the case of the silicone-modified alkyd resin, the range of 1 to 30% by mass is preferable.
Here, the modification rate represents the blending amount of the modifying agent with respect to the entire modified alkyd resin.

Examples of the crosslinking agent used for crosslinking the modified alkyd resin include an urethane resin, an epoxy resin, an acrylic resin, and a phenol resin in addition to an amino resin such as a melamine resin and a urea resin.
In order to sufficiently perform crosslinking, the amount of these crosslinking agents used is preferably in the range of 30 to 90 parts by mass, particularly preferably in the range of 40 to 90 parts by mass with respect to 100 parts by mass of the modified alkyd resin.

The cross-linking of the modified alkyd resin is preferably performed in the presence of an acidic catalyst. There is no restriction | limiting in particular as this acidic catalyst, It can select suitably from well-known acidic catalysts conventionally known as a crosslinking reaction catalyst of an alkyd resin. As such an acidic catalyst, for example, an organic acidic catalyst such as p-toluenesulfonic acid and methanesulfonic acid is suitable.
This acidic catalyst may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, in order to perform a crosslinking reaction efficiently, the usage-amount is preferable 0.1-20 mass parts with respect to a total of 100 mass parts of modified alkyd resin and a crosslinking agent, Especially 0.5-15 mass parts. The range of is preferable.

  The modified alkyd resin, the crosslinking agent and the acidic catalyst as described above are added to an organic solvent at a predetermined ratio together with various additive components used as desired, and a solid content concentration suitable for coating, usually 0.1 to An antifouling layer-forming coating solution adjusted to 10% by mass is applied onto a plastic film substrate and subjected to a crosslinking reaction to form an antifouling layer.

  The organic solvent used at this time can be appropriately selected from known solvents that have good solubility in each compounding component and are inert to them. Examples of such a solvent include toluene, xylene, methanol, ethanol, isobutanol, n-butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. These may be used singly or in combination of two or more.

  Examples of the various additive components used as desired include ultraviolet absorbers, antioxidants, leveling agents, antistatic agents, matting agents, and antifoaming agents.

The antifouling layer forming coating solution prepared in this way, for example, bar coating method, reverse roll coating method, knife coating method, roll knife coating method, gravure coating method, air doctor coating method, doctor blade coating method, etc. Coating on a plastic film substrate by a conventionally known coating method, and crosslinking and curing by heating at a temperature of about 100 to 160 ° C. for 0.2 to 5 minutes to form an antifouling layer Can do.
The thickness of the antifouling layer thus formed is preferably 0.01 μm or more in order to provide durability of the coating film, and 10 μm or less in order to improve the adhesion to the substrate. Is preferred. That is, the thickness of the antifouling layer is preferably in the range of 0.01 to 10 μm, particularly preferably in the range of 0.1 to 5 μm.

In the present invention, the pressure-sensitive adhesive layer is formed on the plastic film surface of the antifouling protective film of the present invention obtained as described above, that is, on the surface of the plastic film substrate where the antifouling layer is not formed. An antifouling adhesive protective film is also provided.
The pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include ordinary pressure-sensitive adhesives such as acrylic, silicone-based, rubber-based, and urethane-based, but are resistant to weather and transparency. Is preferably an acrylic pressure-sensitive adhesive.

As the acrylic pressure-sensitive adhesive, those obtained by copolymerizing a (meth) acrylic acid alkyl ester monomer having an alkyl group having 4 to 12 carbon atoms as a main component and another vinyl monomer copolymerizable therewith are used. Is appropriate.
Examples of the (meth) acrylic acid alkyl ester monomer having 4 to 12 carbon atoms in the alkyl group include butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Isooctyl (meth) acrylate, decyl (meth) acrylate, and the like. The vinyl monomer copolymerized therewith is used to adjust the adhesive strength and cohesive strength of the resulting adhesive, and specifically, for example, (meth) having an alkyl group with 1 to 3 carbon atoms. Examples include acrylic acid alkyl esters; hydroxyl group-containing acrylic acid alkyl esters; α, β-unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, and maleic acid; acrylamide; acrylonitrile; styrene; vinyl acetate;

In the acrylic pressure-sensitive adhesive, a crosslinking agent such as an isocyanate crosslinking agent, an epoxy crosslinking agent, a metal chelate crosslinking agent, or an aziridine crosslinking agent is blended.
The blending amount of the crosslinking agent is preferably in the range of 0.5 to 30 mmol, particularly preferably in the range of 1 to 20 mmol in terms of the functional group equivalent of the acrylic copolymer in order to obtain the required adhesion.

  In the pressure-sensitive adhesive, a tackifier, a filler, an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a colorant, a flame retardant, an antistatic agent and the like are conventionally blended as necessary. It is optional to include various additives, but especially assuming that it is exposed for a relatively long time outdoors, an antioxidant, a UV absorber, and a light stabilizer that have a function of improving weather resistance. It is recommended to add such additives.

  The thickness of the pressure-sensitive adhesive layer (after drying) is preferably 5 μm or more in order to obtain sufficient adhesiveness (tack) and adhesive force, paste bleeding from the film edge, adhesion of dust, In order to prevent the pressure-sensitive adhesive layer from causing cohesive failure at the time of peeling and causing adhesive residue, it is preferably 40 μm or less. That is, the thickness of the pressure-sensitive adhesive layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm.

  The method of providing the pressure-sensitive adhesive layer may be applied directly to the plastic film surface of the antifouling protective film, or after the pressure-sensitive adhesive is applied to the release material, the pressure-sensitive adhesive layer is applied to the marking film substrate surface. You may combine them. Here, as a method for applying the pressure-sensitive adhesive, conventionally known coating methods such as a bar coating method, a reverse roll coating method, a knife coating method, a roll knife coating method, a gravure coating method, an air doctor coating method, a doctor blade coating method, etc. A construction method is mentioned.

The present invention also provides an outdoor marking film in which the antifouling adhesive protective film of the present invention obtained as described above is affixed to the surface.
However, the antifouling protective film of the present invention is particularly effective when applied to an outdoor marking film. However, the present invention is not limited to this, and the antifouling property and surface protection of window glass, show windows, liquid crystal displays, labels, etc. It can be widely used for various objects that require

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Various tests and evaluations in Examples and Comparative Examples were performed by the following methods.

(1) Accelerated weather resistance test About an antifouling adhesive protective film adhered to the surface of a glass plate with an adhesive layer in contact with it, a sunshine super long life weatherometer (Suga Test Instruments, model: WEL-SUN- HCH) was used to conduct a 50 hour accelerated weathering test (exposure test).

(2) Water repellency For a film having an antifouling adhesive protective film adhered to the surface of a glass plate with an adhesive layer in contact, a contact angle measuring instrument (Kyowa Interface Chemical Co., Ltd., model: CA-X150) is used to prevent A water droplet was dropped from the microsyringe onto the antifouling layer surface of the dirty protective film, and the contact angle was measured.

(3) Chemical resistance For the antifouling adhesive film attached to the surface of the glass plate in contact with the adhesive layer, the antifouling layer surface of the antifouling protective film is made of a cloth soaked with toluene or ethanol. The change in the surface state when wiping 10 times (10 reciprocations at 15 cm each way) was visually observed and evaluated according to the following criteria.
○: No change is seen.
X: Peeling from the base material of the antifouling layer is observed.

(4) Adhesion of the antifouling layer The antifouling layer surface of the antifouling protective film was polished with a friction tester (“RT-200” manufactured by Daiei Chemical Seiki Seisakusho Co., Ltd.) and polished with unstretched polypropylene having a thickness of 80 μm as an abrasive piece. The test was conducted under the conditions of a load of 1 kg and a polishing frequency of 50 reciprocations, and the change in the surface condition was visually observed and evaluated according to the following criteria.
○: No fogging or falling off of the antifouling layer is observed.
Δ: Slight fogging or falling off of the antifouling layer is observed.
X: Many antifouling layers are cloudy and fall off.

(5) Antifouling antifouling adhesive film with an adhesive layer attached to the surface of the glass plate is left outdoors and visually observed for contamination of the antifouling layer after one month. Evaluation was made according to the following criteria.
○: Stain of the antifouling layer is hardly seen.
X: Dirt of the antifouling layer is clearly seen.

Example 1
100 parts by mass of a mixture of stearic acid-modified alkyd resin and methylated melamine resin (manufactured by Hitachi Chemical Co., Ltd., trade name: Tesfine 303, solid content 50% by mass) and 1 part by mass of p-toluenesulfonic acid were dissolved in toluene. An antifouling layer-forming coating solution having a solid content of 5% by mass was obtained.
This antifouling layer forming coating solution was applied to the surface of a 50 μm thick PET film (trade name: Lumirror, manufactured by Toray Industries, Inc.) using a Mayer bar, heated at 150 ° C. for 2 minutes, An antifouling layer having a thickness of 0.5 μm was formed.
Thereafter, an acrylic adhesive (trade name: PL Thin, manufactured by Lintec Co., Ltd.) was applied to the opposite surface of the PET film using an applicator, heated at 100 ° C. for 1 minute, and an adhesive layer having a thickness of 20 μm. Formed.
The obtained antifouling adhesive protective film was measured and evaluated for water repellency and chemical resistance before and after the accelerated weathering test, adhesion of the antifouling layer, and antifouling properties, and the results are shown in Table 1.

Example 2
A coating solution for forming an antifouling layer is a silicone-modified alkyd resin obtained by adding 20% by mass of a dimethylpolysiloxane having a phenyl group-substituted alkyl group to a mixture of an alkyd resin and a methylated melamine resin (trade name: KS, manufactured by Shin-Etsu Chemical Co., Ltd.). -882, solid content 50% by mass) 100 parts by mass and p-toluenesulfonic acid 1 part by mass were dissolved in toluene and changed to a coating solution having a solid content of 5% by mass in the same manner as in Example 1. The antifouling adhesive protective film was obtained.
The obtained antifouling adhesive protective film was measured and evaluated for water repellency and chemical resistance before and after the accelerated weathering test, adhesion of the antifouling layer, and antifouling properties, and the results are shown in Table 1.

Comparative Example 1
Except not forming an antifouling layer, it implemented similarly to Example 1 and obtained the adhesion protective film (PET film with an adhesion layer).
The obtained adhesive protective film was measured and evaluated for water repellency, chemical resistance and stain resistance before and after the accelerated weathering test. The results are shown in Table 1.

Comparative Example 2
An antifouling layer-forming coating solution was prepared by adding 100 parts by mass of fluorosilicone (manufactured by Toray Dow Corning Silicone Co., Ltd., trade name: SYL-OFF Q2-7785), a hydrosilane addition type crosslinking agent (Toray Dow Corning Silicone Co., Ltd.) Product name: SYL-OFF Q2-7560) 4 parts by mass and 4 parts by mass of chloroplatinic acid (manufactured by Toray Dow Corning Silicone Co., Ltd., trade name: BY24-808) are dissolved in heptane to obtain a solid content of 5 Except having changed into the solution made into the mass%, it implemented similarly to Example 1 and obtained the antifouling adhesion protection film.
The obtained antifouling adhesive protective film was measured and evaluated for water repellency and chemical resistance before and after the accelerated weathering test, adhesion of the antifouling layer, and antifouling properties, and the results are shown in Table 1.

Comparative Example 3
An antifouling layer-forming coating solution was prepared by adding 100 parts by mass of a non-modified alkyd resin (manufactured by Hitachi Chemical Co., Ltd., trade name: Teslac 2403-60, solid content 60% by mass) and methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd., (Product name: Nicalac MX-750LM, solid content: 75.5% by mass) Except for changing to 120 parts by mass, an antifouling adhesive protective film was obtained in the same manner as in Example 1.
The obtained antifouling adhesive protective film was measured and evaluated for water repellency and chemical resistance before and after the accelerated weathering test, adhesion of the antifouling layer, and antifouling properties, and the results are shown in Table 1.

  From Table 1, the antifouling adhesive protective film of the examples has good chemical resistance, adhesion of the antifouling layer, and antifouling properties, and has an antifouling function even when subjected to long-term outdoor exposure. It is clear that it does not decrease.

Claims (5)

An antifouling protective film in which an antifouling layer comprising a cross-linked product of an oil and fat modified alkyd resin, a fatty acid modified alkyd resin or a silicone modified alkyd resin is formed on a plastic film substrate. The antifouling protective film according to claim 1, wherein the antifouling layer has a thickness of 0.01 to 10 μm. The cross-linked product of an oil- and fat-modified alkyd resin, a fatty acid-modified alkyd resin, or a silicone-modified alkyd resin is crosslinked using an amino resin, a urethane resin, an epoxy resin, an acrylic resin, or a phenol resin as a crosslinking agent. The antifouling protective film according to any one of -2. The antifouling protective film according to any one of claims 1 to 3, wherein an adhesive layer is formed on a surface of the plastic film substrate on which the antifouling layer is not formed. An outdoor marking film, wherein the antifouling adhesive protective film according to claim 4 is adhered to the surface.