JPS5931459B2 - pine film - Google Patents

Description

[Detailed description of the invention] The present invention relates to a matte film.

More specifically, the present invention relates to a matte film that uses a plastic film as a support and has a matte layer on at least one surface, thereby exhibiting excellent writing properties with a pencil, erasability with an eraser, and solvent resistance. Conventionally, a plastic film is used as a support and glass powder, silica powder,
Matte films with matte layers containing matting agents such as clay powder and titanium oxide include polyester films,
polycarbonate film, polyvinyl chloride film,
Matte films using polyethylene films, cellulose triacetate films, etc. as supports are used. The properties required for this matte film include ease of writing with pencils, glass squares, ballpoint pens, fountain pens, magic ink, etc., ease of erasing with erasers, etc., and solvent resistance when correcting and erasing with various solvents after writing with ink, etc. Gender, etc. are required. Practically speaking, matte films are, for example, 7 to
Even if you write strongly with a 9H hard pencil, the matte layer must not peel off and you can write smoothly. Furthermore, when erasing with an eraser or the like after adding with a pencil, it is desirable that the marks be completely erased.
Furthermore, when wiping off with a solvent for correction after adding ink or the like, there must be no problem such as the matte layer peeling off. Conventionally known matte films are made by dispersing the above-mentioned matting agent in polyester, cellulose acetate resin, etc.
It can be obtained by coating a film, or subbing with a film swelling agent and a hydrophilic resin, and further coating the surface with a matting agent dispersed in the hydrophilic resin. Alternatively, in order to improve solvent resistance, matte films have been obtained by dispersing and coating a matting agent in a thermosetting resin. However, these matte layers have poor adhesion between the plastic film and the matte layer, resulting in problems such as the matte surface peeling off when recording with a hard pencil. Many of them had drawbacks such as poor erasability, poor solvent resistance, or yellowing of the matte layer by ultraviolet rays. As a result of repeated research, the present inventors have found that an undercoat layer is provided by applying a liquid containing a polyol resin and/or polyisocyanate and a film swelling agent to at least one surface of a plastic film. It has been found that a matte film provided with a coating layer containing a polyol resin, a polyisocyanate, and a matting agent is excellent without having the above-mentioned drawbacks.

In other words, the adhesion between the support film and the undercoat layer is very good due to the film swelling agent, and the adhesion between the undercoat layer and the matte layer is also due to the reaction between the polyol resin of the undercoat layer and the polyisocyanate of the matte layer or the undercoat layer. It is very strong due to the reaction between the polyisocyanate of the layer and the polyol resin of the matte layer, and the matte layer itself is also very strong due to the reaction of the polyol resin of the matte layer and the polyisocyanate, and firmly fixes the matting agent.

Therefore, the film strength is very strong, and there is no problem of the matte layer peeling off even if you write with a 7-9H hard pencil.The urethane resin, which is a reaction product of polyol resin and polyisocyanate, is hard and easy to write on. Or, it has excellent erasability with an eraser. Furthermore, the matte layer uses a reactive polymer and is cured, so it has excellent solvent resistance.
Even if various solvents are used for correction and erasure after adding ink, etc., problems such as peeling of the matte layer will not occur at all. Furthermore, there is almost no problem of yellowing of the film due to ultraviolet rays. The matte film of the present invention can be applied to a wide range of applications such as tracing films and photosensitive films for second originals. To explain the present invention in more detail, a solution prepared by dissolving a polyol resin and/or a polyisocyanate film swelling agent in an appropriate solvent that dissolves them is applied to at least one surface of a plastic film such as polyester using a kiss coater or the like. Apply it using a paint and dry it at an appropriate temperature.

The ratio of the film swelling agent to the polyol resin and/or polyisocyanate used in this undercoat layer varies depending on the one used or the film base, but the weight ratio is 1:1 to 30:1, particularly 10:1. Shows the best adhesion in the vicinity. In this case, if the amount of the film swelling agent is too large, the swelling effect will be too strong and the flatness of the undercoated film will be impaired, and if the amount is too small, the adhesion will be poor. When using polyol resin and polyisocyanate together, their weight ratio is 1
:1 to 20:1 is preferable. It is appropriate that the coating amount of the F coating layer after drying is in the range of 0.01 to 1.0 y/i. Furthermore, on the surface provided with the undercoat layer, a polyol resin and a polyisocyanate are dissolved in a solvent that dissolves these two, a matting agent is added thereto, and the coating liquid is dispersed using ultrasonic waves or a special means such as a ball mill. Apply using an air knife coater, etc. Dry to obtain a matte layer. After drying, 100℃
When curing for about 30 minutes or leaving it at room temperature for about a week, the polyol resin should be cured between the coating layer and the matte layer, in the matte layer, or in the undercoat layer if polyol resin and polyisocyanate are used together in the coating layer. The reaction between the polyisocyanate resin and the polyisocyanate resin progresses, and an excellent matte film is obtained. When using a polyol resin in the undercoat layer, the polyisocyanate in the matte layer also reacts with the polyol resin in the undercoat layer to improve the adhesion between the paint layer and the matte layer. A sufficient amount is required to react with both polyol resins in the layer.If polyisocyanate is used in the undercoat layer, there is no problem because the polyol resin in the matte layer is not completely crosslinked by the polyisocyanate in the matte layer. In addition, when polyisocyanate and polyol resin are used together in the undercoat layer, it is thought that the polyol resin in the undercoat layer reacts with the polyisocyanate in the coating layer and the matte layer.The polyol resin and polyisocyanate in the matte layer The ratio by weight varies depending on the coating amount and the composition of the undercoat layer, but is 1:1 to 20 by weight.
:l is preferred, particularly 3:1 to 10:1. In this case, if the amount of polyisocyanate is too large, unreacted polyisocyanate remains in the matte layer, causing a problem of stickiness on the coated surface. Furthermore, if the amount of polyisocyanate is too small, crosslinking will be insufficient and solvent resistance will deteriorate. The ratio of matting agent and polyol resin in the matting layer is 1:0.5 to 1:0.5 by weight.
1:20 is preferable, and 1:1 to 1:10 is particularly preferable. If the amount of the matting agent is too small, the surface of the matte layer will have few irregularities, and the writing and erasing properties will be poor. If the amount is too large, the film strength will be weakened and the light transmittance of the matte film will be poor.
Also, the coating amount of the matte layer after drying is 1 to 10y/? -r?
is appropriate. Among the embodiments of the undercoat layer of the present invention, a combination of a polyol resin and a film swelling agent exhibits particularly excellent effects. Film bases used in the present invention include polyester, polycarbonate, polyvinyl chloride, cellulose triacetate, polyolefin and the like, with polyester films being preferred due to their dimensional stability and the like.

The thickness of the film varies from about 30μ to 200μ depending on the application.
Various types can be used, up to the μ level. In addition, polyisocyanate has two or more isocyanate groups in its molecule and is available under the trade name Desmodyur T from Bayer AG of West Germany.
)Desmodyur M)Desmodyur R)Desmodyur TT)Desmodyur H)Desmodyur 15, or trade name of DuPont, USA, Pyren T, Pylen D
There are products known as Millionate MT) Millionate MR) Coronate L, Coronate HL) Coronate 2030 manufactured by Nippon Polyurethane Industries Co., Ltd., and these products include tolylene diisocyanate, diphenylmethane, 4,4' -diisocyanate, triphenylmethane-P,p',p''-triisocyanate, 2,4-tolylenetimer, hexamethylene-1
, 6-diisocyanate, naphthalene-1,5-diisocyanate, dicyclohexamethane-4,4'-diisocyanate, polymethylene polyphenyl diisocyanate, polyisocyanate reacted with 3 moles of tolylene diisocyanate and 1 mole of trimethylolpropane. However, these are not intended to limit the present invention.

Among these polyisocyanates, aliphatic polyisocyanates are particularly excellent in that they are less prone to yellowing due to ultraviolet light and the like.
Polyol resin is a resin having two or more hydroxyl groups in one molecule, and includes polyethylene glycol, polyester having a hydroxyl group at the end, polyether, acrylic, etc. Polyurethane Kogyo product names Desmofene 800, Desmofen 1100, Nituporan 10
04, Nitsuporan 3023, Nitsuporan 121, Excelol 100, and Epiclon 730 (trade name, manufactured by Dainippon Ink and Chemicals). Among these, especially Akuri. Polyol resins are preferred. Next, film swelling agents vary depending on the film base used, but for example, cresol, halogenated phenol, trichloroacetic acid, etc. are used for a polyester film base, and benzyl alcohol, furfuryl alcohol, etc. are used for a polycarbonate or polyethylene film base. , cyclohexane, dimethylformamide, ethyl acetoacetate, methyl carbitol, carbitol acetate, etc., benzyl alcohol etc. for acetate film base (triacetate, diacetate), and polyolefin film base (polyethylene, polypropylene) at around 60°C. Heated dimethylformamide, dimethyl sulfoxide, cellosolve acetate, etc. can be used. Next, as a solvent for dissolving the polyol resin and polyisocyanate, any solvent that dissolves these two can be used, and specifically, methyl ethyl ketone, ethanol, ethyl acetate, butyl acetate, toluene, acetone, xylene, and monochlorobenzene can be used. Examples include halogen-based solvents such as.

Matting agents include glass powder, silica powder, clay powder,
Examples include titanium oxide, starch, fused alumina fine powder, etc.
Those having an average particle diameter of 0.1 to 50 microns are used, and those with an average particle diameter of 1 to 10 microns are particularly preferred. Among these, silica powder exhibits particularly excellent effects. Further, Examples will be described to specifically explain the present invention.

Example 1 A liquid Excelol 10050% toluic acid Butyl solution (manufactured by Nippon Polyurethane Industries, Acrylic polyol) 0.5V Ethyl acetate 5.0V Toluene 5.0Vp -Chlorphenol 1.0VB liquid Excelol 10050% toluene acetic acid Butyl solution 4.0V Ethyl acetate 5V Toluene 5.09 Coronate HL 75% ethyl acetate solution (Manufactured by Nippon Polyurethane Industries. 1.0V Hexamethyl diisocyanate-based polymer (liisocyanate) Thyroid 721.0V (Manufactured by Fuji Davison Chemical.

Fine powder silica) A coating amount after drying on a 75μ polyester film base is 0.1y/7r? Kiss-coat it, dry it with a hairdryer, and then apply a coating on the surface.
Is the coating amount of liquid B (liquid B is dispersed by ultrasonic waves) 4t/n after drying with a coating rod? Apply it so that it becomes
Dry with a hair dryer.

Thereafter, this matte film was cured at 100° C. for 30 minutes. The matte film thus obtained does not peel off even when written with a 9H pencil, and has excellent writing properties. It also has excellent erasability with an eraser. It is also easy to add notes using ink, ballpoint pen, etc. Furthermore, even when the matte film is applied to solvents such as acetone, alcohol, methyl ethyl ketone, ethyl acetate, and tetrahydrofuran, the matte layer does not peel off and has excellent solvent resistance. Similarly, excellent results can also be obtained with samples left at room temperature for one week without curing. Example 2 A matte film was obtained in the same manner as in Example 1, except that a polycarbonate film base was used in place of the polyester film in Example 1, and dimethylkylamide was used in place of p-chlorophenol in Solution A.

Similar to Example 1, this matte film was also very excellent. Example 3 Liquid A Nitsuporan 125 65% ethyl acetate solution (manufactured by Nippon Polyurethane Kogyo Co., Ltd., 0.5y saturated polyester containing trimethylolpropane and phthalic acid as main components) Ethyl acetate 5V Toluene 5y p-chlorophenol 1y B liquid Nitsuporan 125 65% ethyl acetate solution 5.0y Coronate L 75% ethyl acetate solution (manufactured by Nippon Polyurethane Industries. 1.0? 3 mol, polyisocyanate made by reacting tolylene diisocyanate and 1 mol trimethylolpropane) Ethyl acetate 5y Toluene 5y Glass powder (average particle size 2-5μ) The coating amount of liquid A after drying on a 0.5y50μ polyester film is 0.5y. IV
/Wi' after coating and drying, the amount of coating after drying of liquid B (liquid B is dispersed and mixed by ultrasonic waves) is 5V/Rr? The coating was dried and cured at 100° C. for 30 minutes.

The matte film also exhibited excellent writing properties, eraser erasability, and solvent resistance. Example 4 Excelol 100 of Part A of Example 1) 50% toluene.

Coronate L ethyl acetate 75% instead of butyl acetate solution
A matte film was obtained in the same manner as in Example 1 using the solution.
This matte film also showed good results. Example 5 Coronate HL ethyl acetate 75 was added to Solution A of Example 1.
A matte film was obtained in the same manner as in Example 1 by adding 0.051% solution.

This matte film also showed good results. Example 6 Copolymer of vinyl acetate and crotonic acid 10y) Urea formaldehyde resin IOV, fine particle silica 5V, methyl cellosolve 100 on one side of a 50μ polyester film
C. An undercoating process was performed using an undercoat liquid consisting of C, and a matte layer was applied to the back side in the same manner as in Example 1.

A diazo photosensitive solution having the following formulation was applied to the undercoated surface and dried to obtain a second diazo original. The diazo second original was combined with the diazo photosensitive layer, exposed to light under a fluorescent lamp, and then developed with ammonia to obtain a second original. The back surface (i.e., matte layer) of this second original had excellent retouchability, eraser erasability, and solvent resistance, and had good light transmittance, and the printing of the diazo paper using this second original was very excellent. Diazo photosensitive liquid composition Methyl cellosolve 95cr Sulfosalicylic acid 1.0y Zinc chloride 0.21m -Oxyethylphenol 1.01 Resorcin 0. IV 3-Sulfonic acid-1-oxynaphthalene-8-sulfonic acid methylamide 0.2yp-morpholinobenzenediazonium.

BF4O. 7y Cellulose acetate butyrate 2.0V.

Claims (1)

[Claims] 1. An undercoat layer is provided by applying a liquid containing a polyol resin and/or polyisocyanate and a film swelling agent to at least one surface of a plastic film, and the undercoat layer contains a polyol resin, a polyisocyanate, and a matting agent. A matte film characterized by being provided with a coating layer.