JPS60262871A - Coating composition and production of drafting film by using the same - Google Patents

Abstract

PURPOSE:To provide the titled compsn. giving a drafting film which does not cause spreading, blotting nor fading of ink, by dissolving a specified acrylic resin and an N-methoxymethylated nylon resin in an aliph. lower alcohol (aq. soln.). CONSTITUTION:A copolymer obtd. by solution-polymerizing dimethylaminoethylamine (meth)acrylate obtd. from a lower alkyl (meth)acrylate and a dialkylhydroxyethanolamine and a (meth)acrylic monomer in the presence of a catalyst in a lower aliph. alcohol is brought into contact with a hydrogen halide to obtain an acrylic resin (A) contg. a repeating unit of formula I (wherein R1, R2 are each CH3, C2H5; X is halogen; l is 2-4) and a quaternary ammonium group on the side chain of the repeating unit. 0.1-5wt% of a mixture of 100-30pts.wt. component A and 0-70pts.wt. N-methoxymethylated nylon resin (B) contg. a repeating unit of formula II and having a degree of substitution of methoxymethyl group of at least 18% are dissolved in an aliph. lower alcohol or a mixture thereof with water to obtain a coating compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a coating composition and a method for producing a drafting film using the same. More specifically, the present invention provides a coating composition suitable for coating a roughened film, and a coating composition that has excellent aqueous ink receptivity, water resistance, and antistatic properties by applying this coating composition to the rough surface of a roughened film. provide a covering,
The present invention relates to the ability to produce a drafting film that does not cause ink thickening, bleeding, or blurring, and has antistatic properties.

Conventional technology Shingumi tray sink paper has traditionally been used as a base material for drafting.
In recent years, M1 products such as high-grade drafting paper 4 have been used, and in recent years, long-term storage properties have become particularly required for high-grade drafting. However, the # product has dimensional stability due to its hygroscopicity.

Roughened films based on 4-lyester films are recommended for long-term storage or highly used drawings because they have poor mechanical strength and many drawbacks such as yellowing due to retention of length 1. The roughened film that has come to be used includes a film obtained by blowing sand on the surface of the film at high speed, a fine inorganic filler, and an organic solvent containing a binder on the side. Kj!m cloth with 11m surface of soluble laminate, newly opened millilum matte film obtained by drying, film surface etched with @Flukaline solvent, etc., or mixed with fine inorganic filler in advance & fat Although it is known that the surface is roughened by forming a film, sandmant film and chemical matte film are commonly used as drafting films.

However, since the rough surface of the Sandmanto film is due to mechanical etching of the surface of the film material, the uneven surface is the polyester film itself. In addition, chemical matte film is made by providing a binder resin layer containing a filler on a polyester film, as described above, but the binder resins include general hardening 7-acrylate phase resin, unsaturated tetrahydrocarbon resin, etc. Thermosetting resins such as polyester resins and 7-mino resins, vinyl chloride copolymer resins, vinylidene chloride copolymer resins,
Acrylic resins, linear polyester resins soluble in organic solvents, fiber yarn resins, etc. are used.

Therefore, the rough surface of both the sand matte film and the chemical matte film is essentially hydrophobic, and the film itself is very easily charged.

To explain these points further, it has been reprinted from the past! ! ! Lines and the like can be inked using general water-based ink on the roughened film for drawings, but the ink thickens and bleeds significantly, and especially when thick solid lines are drawn, both ends of the line are unfavorably spread out. Those who are rich tracers or professional drafters are able to use the above film with their personal skills and experience, but the disadvantage is that it is difficult for those who are relatively inexperienced to use it properly. Furthermore, when the film is charged, it attracts minute dust or eraser debris in the air due to static electricity, and it cannot be easily rubbed off, making it undesirable for drawing uniform and continuous line segments. The disadvantages are that the drawings are not aligned when they are pulled out, and troubles often arise in the transportation and handling of copies.

Therefore, in order to eliminate these drawbacks, for example, a film-forming polymer electrolyte and polyvinyl alcohol are mixed at a weight ratio of 90:10 to 40:60, and a synthetic resin ester John is added to this mixture at a weight ratio of 10 to 30. It has been proposed to produce a roughened film for drafting by treating the surface of the roughened film with a water-based treatment agent containing a weight-free additive (Japanese Patent Application Laid-open No. 133268/1983), but this drafting film When lines are inked with water-based ink, the ink thickens and bleeds, which is still unsatisfactory and is clearly not satisfactory.

Purpose of the Invention As a result of intensive research in order to produce a drafting film that has improved these drawbacks, the present inventor found that coarse coating can bring out the greatest effect on ink thickening and #bleaching, and has developed the present invention. Reached.

An object of the present invention is to provide a coating composition suitable for coating a roughened film and a method for producing a drafting film using the same. Another object of the present invention is to provide a coating composition capable of coating a roughened film with a coating layer having excellent water-based ink receptivity, water resistance and antistatic properties. Still another object of the present invention is to have excellent ink receptivity;
And thick ink.

There is a need to develop a method for producing a drafting film that is free from bleeding, scratches, etc., has excellent antistatic properties, and has long shelf life.

According to the present invention, these objects of the present invention are as follows: 1 The following formula (
1) Acrylic resin (4) containing a repeating unit having a quaternary ammonium salt in the side chain represented by % formula % and the following formula (21 % formula % (2) Component (B) No. 3. i ratio 100: A coating composition characterized by dissolving 1 to 5% by weight of an aliphatic lower furfur or a mixed solvent of the aliphatic lower alcohol and water K O in a proportion of 0 to 3o; and 2 Formula 111 below: 7)l.

11 Here, an acrylic resin (4) containing a repeating unit having a quaternary ammonium salt in the side chain represented by R, and R-, same or different] and the following formula (2) % formula % (2 ) A coating composition prepared by dissolving 0.1 to 5 ffi% of component (B) in a mixed solvent of an aliphatic lower alcohol or a polyaliphatic lower alcohol and water at a weight ratio of 100:0 to 30:0, This is achieved by a method for producing a drafting film, which is characterized in that it is coated on the rough surface of a roughened film and dried.

Component (4) used in the present invention is an acrylic resin containing a repeating unit having a quaternary ammonium salt in the molecular side chain represented by the above formula (11). Ro and R7 in the above formula (1) are methyl or ethyl. and these may be the same or different. Also, X is halogen,
Examples include chlorine and bromine.

This acrylic resin includes, for example, dimethylaminoethylamine (meth)acrylate obtained by reacting lower furkyl acrylate or lower alkyl methacrylate with difluthylhydroxyethanolamine and other lower furkyl acrylate or methacrylic acid. A (meth)acrylic yarn yarn containing a lower furkyl ester is solution polymerized in the presence of a lower aliphatic flucol using a catalyst such as benzoyl peroxide or aliphatic azonitrile, and then the resulting copolymer is treated with a halogen. It can be produced by contacting with hydrogen oxide.

The acrylic resin obtained in this manner is soluble in lower aliphatic alcohols but substantially insoluble in water. The molecular weight of the acrylic resin is preferably 25,000 to 45,000. This is not preferred because the coating film formation properties are poor and the blocking resistance is extremely poor. On the other hand, if the polymer molecular weight is too large, it becomes difficult to apply the composition and the adhesion to the film surface becomes low, so it is not preferred.

A typical example of such an acrylic resin is Nirecon') PQ-5OB (trade name) manufactured by Soken Chemical Co., Ltd.

In addition, component CB) used in the present invention is in the molecular chain!
N containing a repeating unit represented by ifJ notation (2)
-Methoxymethylated nylon resin with furfur soluble properties. In the repeating unit represented by the formula (2), the hydrogen of the amide bond is replaced with a methoxymethyl group. The N-methoxymethylated nylon resin can be produced, for example, by using nylon 6 as a raw material and reacting it with formaldehyde and methanol to chemically modify it and make it alcohol-soluble. K for alcohol solubility increases the substitution rate of the methoxymethyl group to 18%.
The above is preferable, and this substance can be completely dissolved in methyl alcohol. The stability of the methyl alcohol solution improves as the substitution rate of methoxymethyl groups increases, in other words, as the proportion of units represented by the formula (2) increases. As the degree of methoxymethylation increases, the strength and chemical resistance of nylon resin decrease, but on the other hand, it improves flexibility and moisture absorption.

Growth rate etc. will improve. Compatibility with ingredients.

From the viewpoint of solubility in aliphatic low a flucol, the methoxymethyl group 'v, Il is 20 to 40%, more preferably 25%.
~35% is preferred.

A typical example of such N-methoxymethylated nylon resin is Torezin F-30 (manufactured by Teikoku Kagaku Sangyo Co., Ltd.).
Trade name: methoxymethylation degree of about 30%).

The mixing ratio of the above component (8) and component 03) is 100:0
It is a range concavity of ~30 near 0. Ingredient (4) Even when using a single fox,
The film formed on the polyester film has a Chishima angle with respect to water of 72°t, which is thicker than that of the untreated film (65°).
, resulting in an excessively hydrophobic surface layer, which gives favorable results when drawing line segments with water-based inks.

In other words, the ink becomes thicker and the ink becomes a beautiful thin line, and the suitability for inking can be greatly improved.

This contact angle with water is one of the characteristics that greatly influences the thickening and bleeding of ink, and if it is smaller than 65 degrees of untreated ink, it will not be cloudy with water, and line drawings made with water-based ink will become thicker.

The bleeding is large and undesirable. Therefore, in order to obtain good product handling suitability, better results can be obtained by designing the contact angle with respect to water before treatment to be greater than 65°.

When a small amount of Nanaylon resin [component (B)] is added to the acrylic resin [component (4)], the suitability for inking is further improved.

That is, the ink from both ends of the line is eliminated, the density of the drawings is uniform, sharp, and beautiful, and the finished state of the drawing is particularly excellent.

When the weight ratio of () of the components exceeds 70, the antistatic property, which is one of the basic characteristics, decreases. The preferred mixing ratio (weight ratio) is 80:20 to 60:40.

The aliphatic lower furfur used in the present invention includes:
Examples include methanol, alcohol, n-glopanol, and impropanol. The aliphatic lower alcohol may be used alone (or may be used in combination with 281 or more. Furthermore, the aliphatic lower alcohol may be used in combination with water. The water removal is preferably 50% by weight or less,
Furthermore, it is preferably 40i weight % or less, and especially preferably 30 weight % or less.

The concentration of polymer dissolved in such solvent (component concentration and component (
average concentration) is 0.1 to 5% by weight, more preferably 0.2%
˜lx amount'a. Polymer concentration is higher than 5 weight (
This is not preferable because the roughness on the surface of the roughened film is filled in, resulting in poor writing quality (not only does it have a poor writing feel), but also the workability during blocking.

The coating composition can be applied by a conventional coating method. The amount of coating varies depending on the coating method and the uneven surface condition of the roughened film, but it is usually 0.01 to 11 in terms of dry coating amount.
/ m' + more preferably 0.02 to 0.111/-. It is not preferable to apply an excessively large amount, for example, on top of the irregularities of the roughened film, from the viewpoint of lead-striping properties. Furthermore, if the coating amount is too small, suitability for inking and antistatic properties will not be sufficiently developed, and a drafting film with satisfactory characteristics will not be obtained.

The roughened film used in the present invention is a plastic film roughened for drafting purposes, and a roughened polyester film is particularly preferred. This polyester film is obtained by roughening a biaxially oriented film made of aromatic polyester, such as polyethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, etc., using the above-mentioned roughening method (for example, sand matting method, chemical matting method, etc.). O)ru.

The roughness of the surface of the roughened film is a characteristic that greatly affects the suitability for inking, especially in terms of blurring, and JIS B-060
Ra (center line 1 average roughness) measured at 1 is 0.2~
0.9,! Preferably, K O is in the range of 4 to 0.7. If the surface unevenness is extremely large, in other words, the R
If a is extremely large, the ink tends to smudge. For example, when drawing a thin string with Rotlink, the pen tip gets caught on the convex part of the matte surface, causing smudges and splatters on the line segments, making the ink less clear.
+< cannot be achieved, and if the surface is slightly uneven,
In other words, if Ra is extremely small, there will be no ink blurring, but, for example, when drawing lines with a crow's mouth, the writing quality is poor (
Also, when adding or correcting with a pencil, it is not possible to do it smoothly.

The coating composition of the present invention has excellent properties when applied to the rough surface of a roughened film, and furthermore, when applied to the roughened surface, the coating composition provides excellent aqueous ink receptivity, water resistance, and electrostatic properties to the roughened film. It has a % length that allows it to be used as a drafting film that provides antistatic properties and prevents ink thickening, I# smudges, and blurring (in addition, it has antistatic properties).

Friend example The present invention will be further explained below with reference to Examples.

In addition, the characteristic evaluation in the example was performed by the following method.

1) Line segment (1,0 * a + 0.6 square) by crow opening using M-suitable lot link or drafting water-based ink (Pilot Perpetual Line Co., Ltd.!1i Ri).

0.2$lII+) to increase the thickness of the ink, smudge, II!
The uniformity of the pen, the running condition of the pen, and the purity were observed.

◎: Very good ○: Excellent △: Poor Excellent C): Excellent △: Poor quality ×: Inferior 3) Water contact angle A set of goniometers prepared by placing them in an atmosphere of 20°C and 6096RH for 24 hours. (manufactured by Kogakukiki Seisakusho), and drop ion-exchanged water onto this with a micro cylinder so that the diameter does not exceed 2 degrees, and read the contact angle with a microscope 30 seconds after dropping.

Example 1 #L Quaternary ammonium salt-containing acrylic copolymer (molecular weight 40200) Nirecondo PQ-5013 (line starting chemical)
! ! A 50 wt % bath solution was diluted with a mixed solvent consisting of 7 knol/impropanol 40/bo (mk ratio) to prepare a 0.7 wt % coating solution. This treatment solution was applied to a 75 μm film with an Ra of 0.622 in a coating amount (after drying) of ipo, o61/rrX.
A variety of evaluations were conducted to ensure that K; IL L. The results are shown in Table #1.

Example 2: Apply the treatment solution of SA Example 1 to one surface of a 75μ Teijin Yanto matte film with an Ra of 1089 K]mTh1l (after drying)
m cloth so that it becomes o, o6g/m', and evaluate the woodcutter. The results are shown in Table 1.

Example 3 Part 3 of Example 1! l! The amount of liquid applied to the mantle surface of 75μ Teijin Sandmat film with Ra of 0.167 (after drying)
KIiI cloth was applied so that the value was 0.06.9/m', and various evaluations were performed. The results are shown in Table 1.

Example 4 50wt of Nirecondo PQ-50B, an acrylic copolymer containing a 4a7 ammonium salt (molecular weight: 40200)
% bath liquid methanol/isopropanol = 50150 (
diluted with a mixed solvent consisting of a weight ratio of 0.7 wt%
A solution was prepared.

Furthermore, Torezin F-3 has a degree of methoxymethylation of 30%.
0 (trade name: Teikoku Kagaku Sangyo@J) was diluted with a 70°C heated mixed solvent consisting of methanol/inpulpanol = 50150 (weight ratio) to prepare a 0.7 wt% solution.

The above two solutions were mixed and stirred at a mixing ratio of 70:30 to prepare a coating solution. This treatment liquid has an Ra of 0.6
The amount of coating (after drying) on the matte surface of No. 22 75μ polyester sand mat film (manufactured by Naeto) is approximately o, o6y/
='' and various evaluations were performed. The results are shown in Table 1.

Comparative Example 1 Polyamine-based cationic polymer electrolyte PAS-88 (product name: manufactured by Nittobo Co., Ltd.) and crosslinking agent PAS-catF were
Mixed at a kn ratio of 10 (1:10 f), 4 w
A t% PAS88-F aqueous solution was prepared. Furthermore, separately from this, saponification degree 99 mol% f7) + NIJ vinyl flucol bottle A (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.) and hinichloride Inotene copolymer resin emulsion Saran EX 238
0-1 ('1lfJb name: manufactured by Asahi Tau Co., Ltd.) 4% water solubility meter was adjusted, respectively, and these three types of solutions were mixed at a ratio of 90:10:
The mixture was mixed and stirred at a mixing ratio of 10, and the coating was carried out in a water bath. , this treatment solution was treated with Ila of 0.622, 757+g]-
Re/Domanoto film (manufactured by Teijin ■) with a name cloth on the first side of the mano (after drying) is approximately 0.069/m゜It is φ good.
L, evaluated the gods. Seventy mackerel? Shown in Table 11-
0 Comparative Example 2 The glaze of the Sun 1 mantle fins used in Comparative Example 1 was evaluated without treatment.3) The results are shown in Table 1.

Claims (1)

[Scope of Claims] 1. Acrylic resin containing a repeating unit having a quaternary ammonium salt in the side chain represented by the following formula (1) and the following formula (21% formula % (2) ) is dissolved in a mixed solvent of aliphatic lower alfur or aliphatic lower alfur and water at a weight ratio of 100:0 to 30:0 to 0.1 to 511 C. li composition. 2 The following formula fl + CH. ■ An acrylic resin matrix containing repeating units represented by R, R. and having a quaternary ammonium salt in the side chain and the following formula (2) % formula % (B A coating composition prepared by dissolving 1 to 5 weight percent of aliphatic lower alcohol or the aliphatic lower flucono[ and water in a mixed solvent of KO] at a ratio of 100:0 to 30:0 to 0. A method for producing a drafting film, characterized in that the film is coated on the rough surface of a roughened film and dried. 3. The roughness of the roughened film is in the range of Ra from 0.2 to 0.9 as measured by JISB-0601. A method for producing a drafting film according to claim 2, characterized in that: