JP2002256219A - Coating, method for producing the same, coating film, method for producing the coating film and adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a halogen-free thermoplastic resin coating having excellent pigment dispersion and a long pot life, to provide a method for producing the same, to obtain a coating film having excellent flexibility and weather resistance, a method for producing the coating film and to obtain an adhesive sheet having excellent application capability and weather resistance, and combustible by a simple incineration facility. SOLUTION: This coating comprises a dehalogenative polyester resin solution A which is obtained by mixing a solution of a resin having a high acid value having a dispersed pigment with a solution of a resin having a low acid value and is colored with a pigment and a curing agent B having preferably a specified distance between crosslinking points. This method for producing the coating comprises dispersing the pigment to the solution of the resin having a high acid value, mixing the dispersion with the solution of the resin having preferably a low acid value to give the resin solution A and mixing the solution with the curing agent B. This colored dehalogenative polyester resin coating film is obtained by curing the coating. This method for producing the coating film comprises coating a releasable film with the coating in a mixed state of the resin solution A and the curing agent B and curing the film by drying. This adhesive sheet has an adhesive layer on one side of the coating film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint using a halogen-free thermoplastic resin and a method for producing the same, a coating film (film) produced using the paint, a method for producing the coating film, and The present invention relates to a pressure-sensitive adhesive sheet using the coating film, which is suitably used as an indoor or outdoor advertising sticker or a display sticker. The pressure-sensitive adhesive sheet of the present invention also includes a pressure-sensitive adhesive film, and the pressure-sensitive adhesive sheet used for the above-mentioned applications is generally called a marking film in many cases.

[0002]

BACKGROUND OF THE INVENTION Such marking films are generally
Using a vinyl chloride resin film as the base material, knead the pigment into the base material according to the purpose and color it, or print and coat the base material, then apply an appropriate pressure-sensitive adhesive on one side according to the application The adhesive layer is formed by coating, and a release material such as a release paper is attached for the purpose of further protecting the adhesive layer.
At the time of use, the release material is peeled off and the exposed pressure-sensitive adhesive layer is attached to a predetermined portion of the adherend. This marking film is often used outdoors, signboards, advertising towers,
Advertising stickers used for shutters, show windows, etc .; decorative striped stickers used for vehicles such as automobiles and motorcycles and ships such as motor boats; display stickers used for traffic signs, road signs, information boards, etc. Used for applications. For this reason, the marking film is required to have weather resistance and to have appropriate flexibility (shape following property) for attaching to a cubic curved surface.

[0003] Further, a conventional marking film based on a soft vinyl chloride resin film generates hydrogen chloride gas and dioxin when it is incinerated and discarded, so that it cannot be processed with simple incineration equipment. However, there is a problem that the durability of the incineration equipment is reduced. Therefore, recently, there has been an increasing demand for a low environmental load type marking film which can be processed by a simple incineration facility, and various attempts have been made.

For example, Japanese Patent Application Laid-Open No. 3-45672 discloses that
A marking film based on a urethane film as a halogen-free thermoplastic resin is disclosed. That is, in this publication, a crosslinked aliphatic isocyanate-based urethane film is used as a base material, and a marking film obtained by transferring an adhesive to the base material can follow the flexible movement of a flexible adherend. Therefore, it is disclosed that so-called wrinkles and tunnels do not occur.

On the other hand, a marking film is often used outdoors as a colored decorative adhesive sheet, and the above publication also states that a colorful color tone is required.
As a method for producing a urethane film as a substrate, it is described that a casting method or the like is preferable in terms of surface smoothness.

In order to obtain a film colored by the casting method, it is known to first prepare a coating material obtained by dispersing a pigment in a resin solution, cast the coating material on release paper or the like, and dry and cure the coating material.

[0007]

However, in the above publication, there is no specific description of preparing a coating material in which a pigment is dispersed in a urethane-based resin solution. It is not possible to obtain the specific knowledge to do so. According to the study of the present inventors, to disperse a pigment in a dehalogenated thermoplastic resin solution such as a urethane resin or an acrylic resin,
It is preferable that the acid value of the resin solution is high. However, if the acid value is too high, there is a problem that good moldability cannot be ensured because the viscosity increases due to the reaction with the curing agent and the pot life is short.

In view of the above-mentioned problems of the conventional marking film and the problems of the low environmental load type marking film that the present inventors have found, the present invention provides both excellent pigment dispersibility and a long pot life. Filled halogen-free thermoplastic resin paint and its production method, and excellent flexibility (shape following) and weather resistance of the paint film (film) made using the paint, and the paint film (film) It is an object of the present invention to provide a production method and an adhesive sheet which has good workability, cutting property, and weather resistance using the coating film and can be incinerated by a simple incineration facility.

[0009]

In order to achieve the above object, an invention according to claim 1 is characterized in that a pigment-dispersed thermoplastic resin solution having a high acid value and a dehalogenated thermoplastic resin solution having a low acid value. Obtained by mixing with a resin solution,
Dehalogenated thermoplastic resin solution A colored with a pigment
And a curing agent B.

The invention according to claim 2 is to provide a dehalogenated thermoplastic resin solution having a high acid value by adding and dispersing a pigment, mixing the pigment with the dehalogenated thermoplastic resin solution having a low acid value, and mixing the pigment with the dehalogenated thermoplastic resin solution. A method for producing a coating material according to claim 1, wherein a halogen thermoplastic resin solution A is obtained and combined with the curing agent B or mixed with the curing agent B.

According to the third aspect of the present invention, a pigment is obtained by mixing a high acid value dehalogenated thermoplastic resin solution in which a pigment is dispersed and a low acid value dehalogenated thermoplastic resin solution. Provided is a colored dehalogenated thermoplastic resin coating film obtained by mixing and curing the dehalogenated thermoplastic resin solution A and the curing agent B.

According to a fourth aspect of the present invention, a pigment is obtained by mixing a high acid value dehalogenated thermoplastic resin solution in which a pigment is dispersed and a low acid value dehalogenated thermoplastic resin solution. The present invention provides a method for producing a colored dehalogenated thermoplastic resin coating film in which a coating material obtained by mixing the obtained dehalogenated thermoplastic resin solution A and a curing agent B is applied on a release film and dried and cured.

According to a fifth aspect of the present invention, there is provided a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is provided on one surface of the colored dehalogenated thermoplastic resin film.

According to a sixth aspect of the present invention, the pressure-sensitive adhesive sheet according to the fifth aspect is characterized in that the halogen-free thermoplastic resin is an acrylic polyol and the curing agent is a polyisocyanate crosslinking agent having a distance between crosslinking points of 220 to 570. provide.

Hereinafter, the present invention will be described in more detail. Examples of the dehalogenated thermoplastic resin in the present invention, that is, a thermoplastic resin containing substantially no halogen element, include resins having various functional groups, and preferably, for example, acrylic polyols having various hydroxyl groups. The acrylic polyol is a copolymer of a monomer copolymerizable with an acrylic monomer, a methacrylic monomer, or the like, and has a weight average molecular weight of 1,000 to 200,000 and a glass transition temperature Tg of 0 to 100 ° C.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl acrylate, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, and modified caprolactone (meth) acrylate. The monomers copolymerizable with these hydroxyl group-containing monomers include (meth) acrylates of alcohols having an alkyl group having 1 to 12 carbon atoms, specifically, n-butyl (meth) acrylate, (meth) acrylic acid Examples thereof include 2-ethylhexyl, isooctyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, and lauryl (meth) acrylate. These can be used alone or in combination.

In addition to these vinyl monomers, monomers copolymerizable therewith may be copolymerized. Examples of such a monomer include a carboxyl group-containing monomer such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid, an anhydride thereof, and styrene. The acid value of the thermoplastic resin solution can be adjusted depending on the amount of the carboxyl group-containing monomer or the anhydride thereof.

A thermoplastic resin solution having an acid value of 3 to 40 KOH mg / g is usually adjusted by adjusting a ratio of an acid component in the above-mentioned various copolymer components, and a pigment dispersion resin having a high acid value is used. Use as If the acid value of the pigment dispersing resin is lower than 3 KOH mg / g, the pigment dispersibility tends to deteriorate, and if it exceeds 40 KOH mg / g, the water resistance of the entire resin tends to deteriorate. Usually, a thermoplastic resin adjusted to have an acid value of 0.1 to 2 KOHmg / g is used as a main resin. If the acid value of the resin used as the main resin is lower than 0.1 KOHmg / g, the curing speed becomes slow, and if it exceeds 2, the pot life may decrease.

In the method for producing a paint of the present invention, a pigment is added to and dispersed in a dehalogenated thermoplastic resin solution having a high acid value.
When mixed with a dehalogenated thermoplastic resin solution having a low acid value to obtain a dehalogenated thermoplastic resin solution A colored with a pigment, the compounding ratios of the resin having a high acid value and the resin having a low acid value are each solid. It is desirable that the resin having a high acid value is mixed at a ratio of 1 to 20% by weight and the resin having a low acid value is mixed at a ratio of 80 to 99% by weight in terms of minutes. If the mixing ratio of the high acid value resin exceeds 20% by weight, the pot life decreases, and if it is less than 1% by weight, the dispersibility of the pigment deteriorates.

The paint of the present invention is colored with a pigment obtained by mixing a high acid value dehalogenated thermoplastic resin solution having a pigment dispersed therein and a low acid value dehalogenated thermoplastic resin solution. It is composed of a dehalogenated thermoplastic resin solution A and a curing agent B, and the method for producing a coating material of the present invention obtains the thermoplastic resin solution A as described above and combines it with the curing agent B, or Curing agent B
Is to be mixed with That is, the paint of the present invention is in a state before mixing the thermoplastic resin solution A and the curing agent B,
And the state after mixing, and includes any form of paint.

As the curing agent B, an isocyanate curing agent can be suitably used. Since it is a use for a marking film, a trimethylolpropane adduct, a biuret, an isocyanurate, a mixture thereof, or a condensate thereof of hexamethylene diisocyanate, which is an aliphatic isocyanate having good weather resistance, can be particularly preferably used. More preferably, the distance between crosslinking points (weight average molecular weight /
A polyisocyanate having an isocyanate group number of 220 to 570 is preferable in that a base material having appropriate flexibility and good cutting properties can be obtained. As the curing agent B, a mixture of polyisocyanates having a plurality of different distances between cross-linking points is used, and the average distance between cross-linking points is 220 to 570.
It may be such that it becomes as follows.

If necessary, an ultraviolet absorber, especially a benzotriazole-based ultraviolet absorber (UVA) may be added to the above-mentioned paint.
And stabilizers, especially hindered amine light stabilizers (HAL
In addition to stabilizers such as S), an antifoaming agent, a surface conditioner, and the like may be appropriately added and used.

In the method for producing a colored dehalogenated thermoplastic resin coating film of the present invention, a paint in which the colored dehalogenated thermoplastic resin solution A and the curing agent B are mixed is coated with, for example, a comma coater. The film is cast on a release film by a reverse coater, knife coater, spray gun, screen printing, or the like, and dried and cured to obtain a coating film.

The colored dehalogenated thermoplastic resin coating film of the present invention is obtained by mixing a pigment-dispersed high acid value dehalogenated thermoplastic resin solution with a low acid value dehalogenated thermoplastic resin solution. Is obtained by mixing and curing a dehalogenated thermoplastic resin solution A colored by a pigment and a curing agent B, and the thickness of the coating film (film) is usually 20 to 200 microns. , Preferably 40 to 100 microns.

The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer provided on one surface of the above-mentioned colored dehalogenated thermoplastic resin coating film, and is generally laminated with a release material. The total thickness of the resin coating and the pressure-sensitive adhesive layer is 5
0-250 microns. If the total thickness is less than 50 microns, the workability is reduced due to the weakness of the sheet.
If the thickness is more than 50 microns, the ability to follow a cubic curved surface will be poor.

As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer,
Acrylic resin-based, rubber-based pressure-sensitive adhesives, and the like can be mentioned. Since the marking film is assumed to be used outdoors, an acrylic pressure-sensitive adhesive having high weather resistance is preferably used. The pressure-sensitive adhesive of the present invention may be a solvent-type acrylic pressure-sensitive adhesive polymerized in a solvent or an emulsion-type pressure-sensitive adhesive polymerized in water. Alternatively, a block polymerization type pressure-sensitive adhesive obtained by irradiating the monomer mixture with ultraviolet light may be used. The thickness of the pressure-sensitive adhesive layer is preferably from 20 to 50 μm.

The marking film is generally manufactured by applying a pressure-sensitive adhesive to a release material by a quantitative coating method using a comma coater, a reverse coater, or the like, heating and drying, and then laminating the base material layer. Further, the release material for the marking film of the present invention is not particularly limited, and for example, a silicone-coated release paper can be used.
When the dehalogenated thermoplastic resin is an acrylic polyol and the curing agent is a polyisocyanate crosslinking agent having a distance between crosslinking points of 220 to 570, the degree of crosslinking of the thermoplastic resin coating film as a substrate is moderate. This is preferable since an adhesive sheet having appropriate flexibility and good cutting properties can be obtained.

[0028]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the following, simply “parts” means “parts by weight”.
Means

<Example 1> [Preparation of paint] High acid value acrylic polyol: butyl methacrylate 59
, 10 parts of hydroxyethyl methacrylate, 27 parts of methyl methacrylate, and 4 parts of methacrylic acid were polymerized in a separable flask in the presence of a solvent such as ethyl acetate to give a polymer having a weight average molecular weight Mw 8000 (acid value 4.2, (50% solids). Low acid value acrylic polyol: butyl methacrylate 59
Parts, 10 parts of hydroxyethyl methacrylate and 31 parts of methyl methacrylate are polymerized in a separable flask in the presence of a solvent such as ethyl acetate to obtain a weight average molecular weight Mw of 80.
A polymer of 00 (acid value 0.2, solid content 50%) was obtained. Coloring: 15 parts of red pigment diketopyrrolopyrrole (manufactured by Clariant, "DPP Red") was added to 100 parts of a high acid value resin, and dispersed and mixed using a bead mill to prepare a pigment-dispersed resin. (Preparation of Resin Solution A) 10 parts of the colored high acid value resin and 90 parts of the low acid value resin were stirred and mixed with a disper to obtain a dehalogenated thermoplastic resin solution A colored with a pigment. At this time, the hindered amine-based light stabilizer (HALS) "Tinuvin 622" (manufactured by Ciba Specialty Chemicals Co., Ltd.) is added to 100 parts by weight of the total resin content of the high acid value acrylic polyol and the low acid value acrylic polyol at the same time. And 0.2 parts of a benzotriazole-based ultraviolet absorber (UVA) "Tinuvin 327" (manufactured by Ciba Specialty Chemicals Co., Ltd.). (Preparation of paint) For 100 parts of the above thermoplastic resin solution A,
As a curing agent B, 24 parts of an aliphatic polyisocyanate “Sumidur HT” (distance between crosslinking points: 244, weight average molecular weight: 1100, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added, and mixed and stirred to prepare a coating material.

[Preparation of pressure-sensitive adhesive sheet] The above coating material was applied on a PET film by a reverse coater, and dried and cured to obtain a coating film (film) of 40 microns. On the other hand, a two-component curable acrylic pressure-sensitive adhesive was applied to a silicon-coated release paper by a comma coater so as to have a dry thickness of 30 μm to form a film. This was laminated and laminated on a coating film (film) as a base material of the pressure-sensitive adhesive sheet to obtain a target marking sheet having a pressure-sensitive adhesive layer.

<Example 2> In Example 1, the low acid value resin was prepared by mixing 59 parts of butyl methacrylate, 10 parts of hydroxyethyl methacrylate, 30 parts of methyl methacrylate, and 1 part of methacrylic acid in the presence of a solvent such as ethyl acetate. Polymerization is carried out in a seharable flask and the weight average molecular weight Mw 8000
(Acid value 1.0, solid content 50%) was obtained. Except for these, the target marking film was obtained in the same manner as in Example 1.

Example 3 In Example 1, the curing agent used was an aliphatic polyisocyanate "Coronate H".
L "(distance between crosslink points 250, Mw 850, manufactured by Nippon Polyurethane Industry Co., Ltd.) was added in the same manner as in Example 1 except that 27 parts of a target marking film was obtained. <Example 4> A target marking film was prepared in the same manner as in Example 1 except that the mixing ratio of the high acid value resin and the low acid value resin was changed from 10:90 to 15:85. I got

<Comparative Example 1> A marking film was obtained in the same manner as in Example 1 except that the entire amount was replaced with a high acid value resin instead of the low acid value resin to be mixed. <Comparative Example 2> A marking film was obtained in the same manner as in Example 1, except that a low acid value resin was used instead of the high acid value resin for pigment dispersion. Comparative Example 3 The purpose was the same as in Comparative Example 1, except that the curing agent used in Comparative Example 1 was changed to 18 parts of hexamethylene diisocyanate “Desmodur H” (distance between crosslinking points: 84, Mw 168, manufactured by Sumitomo Bayer Urethane Co., Ltd.). Was obtained.

The paints obtained in the above Examples and Comparative Examples
The coating film and the pressure-sensitive adhesive sheet were evaluated by the following methods, and the results are shown in Table 1.

[0035]

[Table 1]

[Evaluation method] <Available time> The paint prepared by the above method after mixing the curing agent is left at room temperature, the viscosity change with time is measured, and the time until quenching is measured. did. <Evaluation of Pigment Dispersibility> The film formed by coating with the paint prepared by the above method was visually evaluated for unevenness. 3: A sheet with good pigment dispersion and no unevenness was produced. 2: Incomplete pigment dispersion occurred, and streak-like unevenness occurred. 1: Dispersion of the pigment occurred, resulting in overall unevenness.

<Cutting Property> The sheet prepared by the above-described method was cut into a cutting machine "C" manufactured by MIMAKI.
G45 "was cut, and the situation was evaluated on a three-point scale. 3: Good cutting can be performed. 2: Fuzzing of the cutting surface occurred in a part. 1: Notable fluffing of the cutting surface occurred.

<Judgment of possible incineration> The sheet prepared by the above method was sampled in a square of 5 cm, burned in a closed container, the combustion gas was collected in a syringe, and the presence of hydrogen chloride and chlorine gas was determined by gas chromatography. Qualitative analysis was performed. ○ ・ ・ ・ Hydrogen chloride and hydrogen gas were not detected × ・ ・ ・ Hydrogen chloride and hydrogen gas were detected

<Workability> Each sheet prepared by the above method was adhered to the peak of a corrugated plate having a quadratic curved surface as shown in FIG. 1, and then pressed into the valley with a special working tool. After leaving this at 23 ° C. for 3 days, the floating state of the sheet was evaluated according to the following criteria. 5: No floating at the valley occurred. 4: The sheet was partially torn at the time of pushing. 3: Slight floating in the valley occurred. 2: The sheet was remarkably torn at the time of pushing. 1: A remarkable floating occurred in the valley. <Dry curability> After the paint prepared by the above method was mixed with a curing agent, it was molded with an applicator to a dry thickness of 40 μm, dried at 110 ° C. for 10 minutes, and the tackiness of the film surface was evaluated in three steps. . 3: no surface tackiness 2: slight surface tackiness 1: significant surface tackiness

[0040]

The paint of the present invention has good pigment dispersibility, has a long pot life when mixed with a curing agent, and can provide a coating film made of a halogen-free thermoplastic resin. ADVANTAGE OF THE INVENTION According to the manufacturing method of the paint of this invention, the pot life is long and the paint with favorable pigment dispersibility is obtained. The pigmented dehalogenated thermoplastic resin coating of the present invention has pigments well dispersed therein,
Since it does not substantially contain a halogen element, the load on the environment is low. According to the method for producing a colored dehalogenated thermoplastic resin coating film of the present invention, it is possible to provide a coating film in which the pigment is well dispersed and the load on the environment is low. Since the pressure-sensitive adhesive sheet of the present invention uses a halogen-free thermoplastic resin coating film as a base material, there is no need for landfill disposal, and since it is a marking film that can be incinerated and disposed of in a simple incineration facility, it has a low environmental impact. Are extremely useful in this field. In particular, the pressure-sensitive adhesive sheet in which the dehalogenated thermoplastic resin is an acrylic polyol and the curing agent is a polyisocyanate-based crosslinking agent having a distance between crosslinking points of 220 to 570 is not only environmentally friendly, but also has weather resistance. Excellent, and the base material has moderate flexibility, so it is excellent in workability and cutting property.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a corrugated plate having a bent surface.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 7/02 C09J 7/02 Z F term (Reference) 4F100 AK01A AK25A AK25H AK25J AK42 AK51A AK51H AL01A AT00B BA02 BA03 BA07 BA07 BA10B BA10C CA02A CA13A CA13C CC00A EH462 EJ082 EJ862 GB90 HB00A JB16A JK13 JK17 JL00 JL01 JL09 JL10A JL13C JL14B YY00A 4J004 AA05 AA10 AA14 AB05 CA06 CC02 DA01 NA01 GA03 GA01 PB13 PC08

Claims (6)

[Claims] 1. A dehalogenated thermoplastic colored with a pigment, obtained by mixing a dehalogenated thermoplastic resin solution having a high acid value in which a pigment is dispersed and a dehalogenated thermoplastic resin solution having a low acid value. Resin solution A and curing agent B
A paint comprising: 2. A dehalogenated thermoplastic resin solution A colored with a pigment by adding and dispersing a pigment to a dehalogenated thermoplastic resin solution having a high acid value and mixing with a dehalogenated thermoplastic resin solution having a low acid value. 2. The method for producing a paint according to claim 1, further comprising: combining with the curing agent B or mixing with the curing agent B. 3. A dehalogenated thermoplastic colored with a pigment, obtained by mixing a dehalogenated thermoplastic resin solution having a high acid value in which a pigment is dispersed and a dehalogenated thermoplastic resin solution having a low acid value. Resin solution A and curing agent B
Are mixed and cured to form a colored dehalogenated thermoplastic resin coating film. 4. A dehalogenated thermoplastic colored with a pigment, obtained by mixing a dehalogenated thermoplastic resin solution having a high acid value in which a pigment is dispersed and a dehalogenated thermoplastic resin solution having a low acid value. Resin solution A and curing agent B
A method for producing a colored dehalogenated thermoplastic resin coating film, which comprises applying a coating material in a mixed state on a release film, followed by drying and curing. 5. A pressure-sensitive adhesive sheet, wherein a pressure-sensitive adhesive layer is provided on one surface of the colored dehalogenated thermoplastic resin coating film according to claim 3. 6. The dehalogenated thermoplastic resin is an acrylic polyol, and the curing agent is a resin having a distance between crosslinking points of 220 to 57.
The pressure-sensitive adhesive sheet according to claim 5, wherein the pressure-sensitive adhesive sheet is a polyisocyanate-based crosslinking agent.