JPH07101022A - Flame retardant coating laminate - Google Patents

Abstract

PURPOSE:To provide a coating laminate which has excellent recording characteristics while holding high heat resistance, hydrolytic resistance, mechanical characteristics, chemical resistance, etc., in a normal polyester film and in which high flame retardance can be imparted, and ranks of UL-94, VTM-2 can be sufficiently performed. CONSTITUTION:A coating laminate comprises a coating layer containing inorganic and/or organic particles and a polymer binder and provided on a support, wherein the coating layer contains a graft copolymer acrylic resin having a main chain of the binder made of a hydrophobic monomer and a branched chain made of a hydrophilic monomer and a cationic polymer as main ingredients, and the support is a polyester film in which linear polyesters A, C having a flame retardant element of 0.5-5.0wt.% and a linear polyester B having a flame retardant element of less than 0.5wt.% are sequentially laminated in a thickness direction in the order of A/B/C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating laminate, and more particularly to a coating laminate applied to various printing sheets such as ink jet, offset printing and flexographic printing. More specifically, while maintaining the characteristics of polyester, US Underwriters Laboratories (UNDERWRITERS LABORATORI
The present invention relates to a flame-retardant coating laminate having a flame-retardant level equivalent to VTM-2 defined by ES) standard UL-94.

In particular, the present invention provides a flame-retardant label laminate having a high flame-retardant property suitable for applications such as caution labels for home electric appliances and vending machines and process control labels requiring flame-retardant properties.

[0003]

2. Description of the Related Art Conventionally, as a coating laminate applied to a printing sheet, there is used a high quality paper, a synthetic paper or a plastic film on which a water-based coating agent comprising inorganic particles and an aqueous binder emulsion is applied. Has been.

[0004]

However, although these coating laminates have good printability, etc., they have insufficient flame retardancy, and thus are used in applications requiring high flame retardancy as described above. Leaves a problem.

An object of the present invention is to provide a coating laminate which has alleviated the above problems, has good printability, and has high flame retardancy.

[0006]

In order to solve the above problems, the present invention provides a support with a coating layer containing inorganic and / or organic particles and a polymeric binder. In the coating laminate, the polymer binder has a trunk layer made of a hydrophobic monomer and a branch chain made of a graft copolymer acrylic resin having a hydrophilic monomer, and a coating layer containing a cationic polymer as main components. Linear polyester A, C whose support contains 0.5 to 5.0% by weight of flame retardant element
And a linear polyester B containing less than 0.5% by weight of a flame-retardant element in the thickness direction in the order of A / B / C, which is a polyester film. It is a summary.

The linear polyester A referred to in the present invention,
B and C are linear polyesters composed of an acid component mainly containing an aromatic dicarboxylic acid and a glycol component. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 4 , 4'-diphenyldicarboxylic acid, 4,4'-
Examples thereof include diphenylethanedicarboxylic acid. Of these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable, and terephthalic acid is particularly preferable.

The glycol component is preferably alkylene glycol, and examples thereof include ethylene glycol, triethylene glycol, tetramethylene glycol, hexamethylene glycol and decamethylene glycol. Of these, ethylene glycol is particularly preferable.

In the present invention, polyethylene terephthalate and polyethylene 2,6-naphthalate are preferable as the linear polyester, and polyethylene terephthalate is particularly preferable.

Further, in the linear polyester in the present invention, a part of the acid component of the above ester or a part of the glycol component is another dicarboxylic acid component such as isophthalic acid, sodium sulfoisophthalic acid, diphenoxydiethanedicarboxylic acid. Acid, adipic acid, sebacic acid, etc., or other glycol component such as diethylene glycol, propylene glycol, trimethylene glycol,
Tetramethylene glycol, neopentyl glycol,
It may be a copolyester substituted with 1,4-cyclohexanedimethanol, polyethylene glycol, a bisphenol A component or the like.

The flame-retardant element (also referred to as a flame-retardant element) is an element such as phosphorus or a halogenated element, or antimony or aluminum which becomes a flame-retardant compound such as antimony trioxide, aluminum hydroxide or tin oxide hydrate. , Elements such as tin, these flame-retardant elements and flame-retardant compounds are described in detail in "Plastic flame-retardant" (written by Eiichi Taita, published by Nikkan Kogyo Shimbun, published in 1978). There is. Of these, phosphorus and halogen elements are preferable, and it is particularly preferable that these elements are copolymerized as a compound with polyester. Particularly, a phosphorus element is preferable, and a phosphorus compound containing a phosphorus element is particularly preferable. Furthermore, it is particularly preferable that the polyester is copolymerized in the polyester or a mixture of the copolymer and the polyester which is not copolymerized.

The preferred phosphorus compound used in the present invention is a phosphorus compound having two ester-forming functional groups, and is a phosphate represented by Chemical formula 7, a phosphinate represented by Chemical formula 8, or a phosphine oxide represented by Chemical formula 9. And so on.

[0013]

[Chemical 7]

[Chemical 8]

[Chemical 9] In the formula, R ₁ and R ₅ are the same or different groups and each represents a hydrocarbon group having 1 to 18 carbon atoms, R ₂ ,
R ₃ is the same or different group and represents a hydrocarbon group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms or a hydrogen atom, and A ₁ , A ₂
Represents a divalent or trivalent organic residue having 2 to 8 carbon atoms, R ₄ represents a carboxy group, a hydroxyl group or an ester thereof, R ₆ represents a carboxy group, a hydroxyl group or an ester thereof, or It represents a divalent ester-forming functional group that forms a ring with A ₂ via a group represented by 10.

[0014]

[Chemical 10] Preferred examples of the phosphorus compound represented by the above Chemical formula 7 include dimethyl phenylphosphonate and diphenyl phenylphosphonate.

Preferred examples of the phosphorus compound represented by the above chemical formula 8 include (2-carboxyethyl) methylphosphinic acid, methyl (2-methoxycarbonylethyl) methylphosphinate, (2-carboxyethyl) phenylphosphinic acid, ( Examples thereof include methyl 2-methoxycarbonylethyl) phenylphosphinate, methyl (4-methoxycarbonylphenyl) phenylphosphinate, (2- (β-hydroxyethoxycarbonyl) ethyl) methylphosphinic acid, and ethylene glycol esters thereof.

Preferred examples of the phosphorus compound represented by the above chemical formula 9 are (1,2-dicarboxyethyl) dimethylphosphine oxide, (2,3-dicarboxypropyl) dimethylphosphine oxide and (1,2-dimethoxycarbonyl). Ethyl) dimethylphosphine oxide,
(2,3-dimethoxycarbonylethyl) dimethylphosphine oxide, (1,2-di (β-hydroxyethoxycarbonyl) ethyl) dimethylphosphine oxide,
(2,3-di (β-hydroxyethoxycarbonyl) ethyl) dimethylphosphine oxide and the like can be mentioned.

Of these compounds, the compound represented by Chemical formula 8 is particularly preferable because it has a good copolymerization reactivity with the polyester and has little scattering during the polymerization reaction. Still other preferred phosphorus compounds are monoalkyl acid phosphates and dialkyl acid phosphates represented by the following chemical formulas 11 and 12, or a mixture thereof.

[0018]

[Chemical 11]

[Chemical 12] (In the formula, R is an alkyl group having 1 to 8 carbon atoms) Of the compounds of the above chemical formula 8, the following chemical formulas 13 and 14 are particularly preferable, and they may be used in combination or in combination with other phosphorus compounds.

[0019]

[Chemical 13]

[Chemical 14] The preferable content of elemental phosphorus is linear polyesters A and C.
Then, 0.5 to 5.0% by weight, more preferably 1.0 to
It is 2.0% by weight, and in the case of the linear polyester B, it is less than 0.5% by weight, more preferably less than 0.2% by weight. The phosphorus element content of the linear polyesters A and C is 0.5% by weight.
If it is less than 5.0% by weight, the effect of flame retardancy is not recognized, and if it exceeds 5.0% by weight, the deterioration of hydrolysis resistance, heat resistance, etc. may cause deterioration of quality, or the melting point may cause deterioration of film quality. Adhesion occurs, making film formation extremely difficult. The phosphorus element content of the linear polyester B is 0.
When it is 5% by weight or more, the quality of the film such as hydrolysis resistance and heat resistance is deteriorated, and the excellent properties of the polyester film are impaired.

The method of adding or copolymerizing the compound containing the flame retardant element to the linear polyester is not particularly limited, but for example, JP-A-51-82392 and JP-A-2-53 can be used.
821, JP-A-63-133589, JP-A-62-27.
It can be carried out by a conventional polymerization method disclosed in Japanese Patent No. 7429.

It is to be noted that conventionally known additives may be added to the linear polyester of the present invention within a range not impairing the object of the present invention. For example, pigments, stabilizers, plasticizers, antistatic agents such as lithium salts of alkylbenzene sulfonates, lubricants, etc., which are commonly used in polyester films, may be added.

The polyester film of the present invention comprises a linear polyester A, a linear polyester B, and a linear polyester C laminated in the thickness direction A / B / C in the case of laminating a coating layer, which will be described later. Flame retardant UL-94, VT
It is essential for conforming to M-2. A / B, B / A
The flame retardancy level is lowered in the configurations such as / C, A / C / B, and B / A / B. The types and amounts of the flame-retardant elements of the linear polyesters A and C may be the same or different, but the same is advantageous in film formation, and in normal use, the front and back of the film can be distinguished. There is no and is preferable.

As a method for laminating the linear polyesters A, B, and C, a method of laminating each other with an adhesive or a method of directly laminating the polymers of each other in a molten state without using an adhesive is used. From the viewpoint of flame retardancy, flexibility as a film, mechanical properties, and processability, it is most preferable to laminate in a molten state.

The thickness of the linear polyesters A and C in the film of the present invention is preferably 0.01 to 3 times, more preferably 0.05 to 1 times the thickness of the linear polyester B, and A , The specific thickness of C is preferably 0.05
˜250 μm, more preferably 1 to 200 μm.
When the thickness of the linear polyesters A and C is less than 0.01 times the thickness of the linear polyester B, or less than 0.05 μm, it does not conform to the intended UL-94 and VTM-2 and exceeds 3 times. If it exceeds 250 μm, the properties required for the polyester film such as heat resistance and hydrolysis resistance cannot be obtained. The linear polyesters A and C may have the same thickness or different thicknesses, but it is preferable that they have the same thickness as possible because there is no difference between the front and back on the film formation and the film. The total thickness of the polyester of the present invention is not particularly limited, but is preferably 10 to 500 μm.

In the present invention, the film oriented in at least one direction means the above-mentioned laminated linear polyester A /
A film in which B / C is oriented in at least one direction, preferably in the longitudinal and lateral directions, and the degree of orientation is not particularly limited, but is defined by the following formula in order to exhibit the characteristics of the polyester film. The birefringence Δ _n of the plane orientation is preferably 0.1 or more.

Δ _n = (nγ + nβ) / 2−nα where n is the refractive index and the subscript αβγ is the three optical axes of the polyester, and nα ≦ nβ ≦ nγ is defined. In the oriented polyester film, α is the thickness direction, β, γ
Is in the plane of the film. The refractive index in three directions can be measured using an Abbe refractometer and an analyzer.

Next, the method for producing the polyester film of the present invention is not particularly limited, but preferably the linear polyesters A, B and C are respectively extruded by extruders A, B and C by a conventional method.
Before being introduced into the T-die, or in the T-die laminating die, three layers of A / B / C are laminated, and the melted sheet is placed on a drum cooled to a drum surface temperature of 10 to 60 ° C. The unstretched film is adhered to individual pieces by electrostatic force,
It is guided to a roll group heated to 0 ° C., longitudinally stretched 2 to 5 times in the longitudinal direction, and cooled by a roll group at 20 to 50 ° C. Subsequently, transverse stretching is performed in a direction perpendicular to the longitudinal direction in an atmosphere heated to 90 to 140 ° C. Stretching ratio is 2 for both length and width
It is stretched 5 times, but its area magnification is preferably 6 to 20 times. If the area magnification is less than 6 times, whitening is not sufficiently performed, and if it exceeds 20 times, tearing tends to occur during stretching. The biaxially stretched film has a thickness of 150 to 24
After heat fixing at 0 ° C. and uniform cooling, the film of the present invention is obtained.

In the polyester film used in the present invention, the linear polyester films A and / or C which are in contact with the coating layer in order to more adhere the linear polyester films A and / or C to the coating layer impair the object of the present invention. Corona discharge processing, urethane resin,
The anchor treatment may be performed using a known anchor treatment agent such as an acrylic resin, an epoxy resin, or a polyester resin.

Particularly, an undercoat of a reaction product of a vinyl-based copolymer having a hydroxyl group and a partial ester group of phosphoric acid and a polyisocyanate compound (Japanese Patent Publication No. 58-3514).
5), or an undercoating composition comprising a hydrophilic group-containing polyester resin grafted with an acrylic compound and a cross-linking agent, improves the adhesiveness between the coating layer and the polyester film layer. It is preferable as a film having excellent durability such as moist heat resistance and boiling water resistance.

The inorganic particles referred to in the present invention are amorphous silica, anhydrous silica, aluminum silicate, magnesium silicate, zinc silicate, calcium silicate, hydrotalcite, zeolite, satin white, titanium oxide, aluminum oxide. , Magnesium oxide, calcium carbonate, calcium sulfate, barium sulfate, diatomaceous earth, kaolin, talc, acid clay, activated clay, bentonite and the like.

Among them, a porous material having pores on the surface of the particles is preferable, and a hollow porous material or a non-hollow porous material capable of freely enclosing and releasing a liquid, a solid or a gas inside thereof has a point of ink absorbability. Is preferred. The method for producing the porous particles is not particularly limited, but representative production methods are shown in JP-A-62-292476, JP-B-54-6251 and JP-B-57-55.
No. 454 and Japanese Patent Publication No. 55-43404, it is a method of adjusting an inorganic powder by "interfacial reactivity", that is, an aqueous solution precipitation reaction. In the adjustment process, a water-in-oil type (W / O Type) Emulsion can be used to prepare hollow, spherical, and porous inorganic powder particles.

Specific examples of the wall material of the inorganic material forming the porous particles include alkaline earth metal carbonates such as calcium carbonate, barium carbonate and magnesium carbonate,
Calcium silicate, barium silicate, alkaline earth metal silicates such as magnesium silicate, calcium phosphate, barium phosphate, alkaline earth metal phosphates such as magnesium phosphate, calcium sulfate, barium sulfate,
Alkaline earth metal sulfates such as magnesium sulfate, silicic acid anhydride, aluminum oxide, zinc oxide, iron oxide, titanium oxide, metal oxides such as cobalt oxide, nickel oxide, manganese oxide, antimony oxide and tin oxide, iron hydroxide ,
Metal hydroxides such as nickel hydroxide, aluminum hydroxide, calcium hydroxide and chromium hydroxide, metal silicates such as zinc silicate, aluminum silicate and copper silicate, zinc carbonate, aluminum carbonate, cobalt carbonate, carbonic acid Typical examples are nickel and basic metal carbonates such as copper carbonate, but among them, those comprising silicic acid anhydride are particularly preferred in the present invention in view of the characteristics of the coating laminate.

The organic particles referred to in the present invention include ion exchange resin powder, urea resin powder, polyethylene resin powder, polystyrene resin powder, urea formalin resin powder, acrylic resin powder, styrene-acrylic resin powder and the like. Among them, peculiar shaped particles of acrylic resin powder and styrene-acrylic resin powder are preferable. Of these, donut-shaped flat particles, aggregated particles of fine particles, core-shell structured particles, hollow porous particles and the like are preferable. Ink absorbability can be increased by using these uniquely shaped particles.

The average particle diameter of the inorganic and / or organic particles is 0.1 to 25 μm, preferably 0.5 to 15 μm,
More preferably, 0.5 to 10 μm is easy to handle,
It is preferable in terms of coatability and printability.

The content of the inorganic and / or organic particles in the coating layer is 100% by weight of the polymer binder,
It is preferably 1 to 100% by weight, preferably 5 to 70% by weight. If the content is less than 1% by weight, the ink setting property becomes insufficient, and if it exceeds 100% by weight, the adhesiveness between the coating layer and the film support tends to decrease.

In the present invention, the polymer binder has a graft copolymerized acrylic resin as a main component, and a different type of monomer is selected for the trunk chain and the branch chain, and the function and the branch chain depending on the function It is a function-separated polymer that also has functions. Among these, by using a hydrophobic polymer for the main chain and a hydrophilic polymer for the branch chain, it is possible to obtain a coating film having hydrophilicity and water resistance. The graft copolymerized acrylic resin as the main component in the present invention means that the polymer itself is 50% by weight or more, preferably 60% by weight in the polymer binder.
The above is indicated, and if necessary, other substances may be added as long as the characteristics are not impaired. In the polymer binder used in the present invention, examples of the monomer unit for introducing the hydrophobic polymer include styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, and (meth) acrylic acid esters. Further, the monomer unit into which the hydrophilic polymer is introduced has a hydrophilic structural portion such as a carboxylic acid group, a sulfonic acid group, a sulfuric ester group, a phosphoric acid group, a hydroxyl group, an amino group and an amide group. In addition to the above monomer units, acrylonitrile, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, N-methylol acrylamide, N-butoxymethyl acrylamide, etc. can be used. Among them, the main chain is methyl methacrylate, the branch chain is hydroxyethyl methacrylate,
And / or a copolymer of N-methylol acrylamide is preferred.

A polymer electrolyte or a conductive powder is usually added to the coating layer in order to adjust the electric resistance of the surface. In the present invention, a cationic polymer such as a quaternary ammonium salt is preferably used as the polymer electrolyte from the viewpoints of electrical conductivity and compatibility with the polymer binder.
Of these, cationic acrylic polymers are more preferably used. Examples of the cationic acrylic polymer include salts of butyl methacrylate and dimethylaminoethyl methacrylate, and specifically, Elecondo PQ-10, PQ-50B, B-149 manufactured by Soken Chemical Industry Co., Ltd. can be effectively used. . In the present invention, the addition of the conductive powder is not particularly limited, but tin oxide, indium oxide, zinc oxide, tantalum oxide, or a combination thereof is preferable.

The coating layer constituting the coating laminate of the present invention has a smoothness of 2 to 5000 seconds, preferably 10 to 3
000 seconds, and more preferably 20 to 2500 seconds. When the smoothness is smaller than that of the present invention, the ink permeation speed is too high and the recording becomes light, which is not preferable. On the other hand, if it is larger than that of the present invention, the ink permeation rate is too low and the ink is likely to remain on the surface of the coating layer, and when the recording surface is rubbed, the recording surface is likely to be contaminated with residual ink, which is not preferable.

The thickness of the coating layer constituting the coating laminate of the present invention is not particularly limited, but is preferably 0.5 to 50 μm, and the thickness in the range of 1.0 to 20 μm is the coating layer. Is desirable in terms of uniform formability and adhesion. Further, the coating layer may optionally contain known additives such as a coating property improver, a thickener, an antioxidant, an ultraviolet absorber and a dye in an amount that does not impair the present invention.

The coating laminate of the present invention comprises a support and a coating layer comprising the above-mentioned composition provided on at least one surface of the support. As a method for providing the coating layer, when the support is a plastic film, the film support to be the base is pre-stretched in the film forming step, and then a liquid adjusted to a predetermined amount is applied,
After that, a method of drying is preferably applied, for example, a method of providing a step of coating-drying after winding as a base film single film.

The solution of the previous composition to be applied is used in the form of an organic solvent solution in order to solve various problems such as water resistance of the coating film and foamability of the coating material. The organic solvent is not particularly limited, but toluene, methyl ethyl ketone, methyl cellosolve, isopropyl alcohol and the like are preferably applied.

The coating method is not particularly limited, but gravure coating method, reverse coating method, reverse gravure coating method, kiss coating method, die coating method, metalling bar coating method, etc. are possible because high speed thin film coating is possible. Known methods can be applied. The coating speed,
The coating film drying conditions are not particularly limited, but it is desirable that the coating film drying conditions be carried out within the range that does not adversely affect various properties of the coating layer and the support.

[0043]

[Evaluation method of physical properties] The evaluation method of the present invention is as follows.

(1) Smoothness Oken type smoothness tester (model KB-15) manufactured by Asahi Seiko Co., Ltd.
It was measured at. The average is shown as n = 5.

(2) Adhesiveness of coating layer The adhesiveness of the coating layer / support is such that a crosscut (100 pcs / cm ² ) is put on the coating layer and the crosscut surface is 45 ° with respect to the crosscut surface: Cellotape: CT- 24 (manufactured by Nichiban Co., Ltd.)
Affix, and use a hand roller to apply a load of about 5 kg to 10
The cellophane tape was forcibly peeled in the direction of 180 ° by pressing back and forth twice, and the degree of peeling of the coating layer was observed and evaluated. The criteria are as follows.

⊚: Very good (no peeling) ○: Good (peeling area less than 5%) Δ: Slightly inferior (peeling area 5% or more and less than 20%) X: Poor (peeling area 20% or more)

(3) Thickness of coating layer The thickness was measured by a micrometer or a dial gauge.

(4) Recording Property Inkjet Personal Computer "98no" manufactured by NEC Corporation
te "is connected to Canon Inc. bubble jet printer" BJ-10V "to print a character pattern,
The print quality and ink absorbency were evaluated, and the recordability was determined as follows. The print quality was evaluated by visual observation with a magnifying glass, and the ink absorbency was measured immediately after printing by touching the character pattern with a finger.
It was rubbed and evaluated based on the degree of contamination of the receiving layer with ink.

⊚: Printing quality and ink absorption are very good. ◯: Printing quality and ink absorption are good. Δ: Printing quality and ink absorption are slightly inferior. X: Printing quality and ink absorption are poor.

Offset printing A printing suitability tester RI-2 type (manufactured by Akira Seisakusho) was used to print offset printing ink TK Mark Five Beni (manufactured by Toyo Ink Co., Ltd.) and the following evaluations were made. It was judged according to the standard. The ink amount was set to 0.3 cc, and the absorptivity was evaluated on the printed surface by OK coated paper (Oji Paper Co., Ltd.).
Made from top) and the line thickness is 353g / c
The time until the ink was not transferred to the OK coated paper was visually evaluated by running a metal roll of m.

⊚: Good (transfer does not occur in less than 15 minutes) ◯: Good (transfer does not occur in 15 minutes or more and less than 30 minutes) Δ: Slightly inferior (transfer does not occur in 30 minutes or more and less than 60 minutes) ×: Poor ( (Transfer after 60 minutes or more)

[0052]

EXAMPLES Next, the present invention will be specifically described by way of examples.

Example 1 Bis-β-hydroxyethyl terephthalate and its low polymer were synthesized from terephthalic acid and ethylene glycol by a direct esterification method to obtain antimony trioxide and (2-
Carboxyethyl) methylphosphinic acid ethylene glycol ester with respect to the polymer phosphorus element amount A and C
After adding 2.0% by weight to the above, a polycondensation reaction was carried out in the usual way to obtain a polyester having an intrinsic viscosity of 0.64 to 0.68. The polymer was heated at 270 to 280 ° C. using extruders A and B.
Melted in a T-die and laminated in the order of A / B / C into 3 layers,
After forming into a sheet on a cooling drum at 28 ° C, 90
Stretched 3.2 times in the machine direction at ℃, then 125 ℃ in the transverse direction
Was stretched 3.3 times and further heat-treated at 225 ° C. to obtain a biaxially stretched film having a thickness of 100 μm.

Next, A of the obtained polyester film
A layer surface corona discharge treatment was performed, and the following coating agent was applied so that the thickness after drying was 10 μm, and dried at 130 ° C. for 2 minutes to obtain a coating laminate of the present invention.

[Coating agent composition] 70 parts by weight (solid content weight ratio) of a graft copolymer acrylic resin (L-40 manufactured by Soken Chemical Industry Co., Ltd.) and a cationic acrylic polymer (Soken Chemical Industry Co., Ltd.)
Manufactured Elecond) 30 parts by weight (solid content weight ratio) and inorganic particles having an average particle diameter of 3.5 μm and a specific surface area of 350 m ² /
g of amorphous silica (Mizukasil P- manufactured by Mizusawa Chemical Co., Ltd.)
78A) 50 parts by weight and a flame retardant (“CR-50” manufactured by Daihachi Chemical Co., Ltd.
9 ") 1 part by weight was diluted with a toluene / methyl ethyl ketone mixed solvent (weight ratio = 1/1) to prepare a 20% by weight coating agent. The properties of this coating laminate are shown in Table 1.
As is clear from Table 1, the coating film strength and the recording property are excellent, and the flame retardancy is rank VTM-2.

Example 2 The phosphorus elements of the polyester used in Example 1 were changed to A and C.
Was added to B and 0.4% by weight to B to obtain a surface porous film of the present invention in the same manner as in Example 1.

The characteristics of this coating laminate are shown in Table 1. As is clear from Table 1, the coating film strength and the recording property are excellent, and the flame retardancy is rank VTM-2.

Example 3 Bis-β-hydroxyethyl terephthalate and its low polymer were synthesized from terephthalic acid and ethylene glycol by a direct esterification method to obtain antimony trioxide and (2-
Carboxyethyl) methylphosphinic acid ethylene glycol ester with respect to the polymer phosphorus element amount A and C
After adding 2.0% by weight to the above, a polycondensation reaction was carried out in the usual way to obtain a polyester having an intrinsic viscosity of 0.64 to 0.68. The polymer was heated at 270 to 280 ° C. using extruders A and B.
Melted in a T-die and laminated in the order of A / B / C into 3 layers,
After forming into a sheet on a cooling drum at 28 ° C, 90
The film was stretched 3.2 times in the machine direction at 0 ° C.

Next, as a water-dispersible polyester copolymer grafted with acrylic, "Peth resin" 604G.
(Takamatsu Yushi Co., Ltd.) was diluted by adding water, and 4 parts by weight of "Nikalac" MW12LF (manufactured by Sanwa Chemical Co., Ltd.) as a cross-linking agent was added to 100 parts by weight of the resin solid content. 0.5 parts by weight of 10 μm silica sol “Cataroid” (manufactured by Catalysis Chemicals Co., Ltd.) was added to 100 parts by weight of the resin solid content, and a coating having a concentration of 3.0% by weight was applied on one side of the uniaxially stretched film. After coating by a bar method, the coating layer is dried and stretched in the transverse direction 3.3 times at 125 ° C., and further heat-treated at 225 ° C., and biaxially stretched with an anchor layer of 0.1 μm to a thickness of 100 μm. I got a film. Next, a coating laminate of the present invention was obtained by using the same coating agent as in Example 1 on the surface of the obtained polyester film on which the acrylic group-grafted hydrophilic polyester resin was undercoated.

The characteristics of this coating laminate are shown in Table 1. As is clear from Table 1, the coating film strength and the recording property are excellent, and the flame retardancy is rank VTM-2.

Comparative Example 1 Table 1 shows only the polyester film obtained in Example 1.
As shown in (1), the flame retardancy was as high as VTM-0, but the recording property was poor. If the coating layer is not applied in this way, a material having excellent recording properties cannot be obtained.

Comparative Example 2 A 100 μm film was obtained in the same manner as in Example 1 except that the phosphorus element was not added to the polyester A and C layers.

Next, A of the obtained polyester film was used.
A coating laminate was obtained by using the same coating agent as in Example 1 on the layer surface.

The characteristics of this coating laminate are shown in Table 1. As is clear from Table 1, the coating film strength and the recording property are excellent, but it is lower than the VTM-2 standard in the flame retardancy test,
It was not possible to obtain high flame retardancy.

[0065]

[Table 1]

[0066]

INDUSTRIAL APPLICABILITY The present invention is a coating laminate having a coating layer laminated on at least one side of a plastic film, and by applying a specific plastic film, a coating having good recording property and high flame retardancy. It was possible to obtain a laminate.

Since the coating laminate of the present invention thus obtained has excellent properties, it has a high flame retardancy suitable for applications such as caution labels for home electric appliances and vending machines and process control labels requiring flame retardancy. UL-
At 94, the VTM-2 rank can be fully achieved.

Claims (10)

[Claims] 1. A coating laminate comprising a support and a coating layer containing inorganic and / or organic particles and a polymeric binder, wherein the backbone of the polymeric binder is composed of a hydrophobic monomer. And a coating layer mainly composed of a graft copolymer acrylic resin having a branched chain of a hydrophilic monomer and a cationic polymer, and the support contains 0.5 to 5 flame-retardant elements.
A polyester film in which linear polyesters A and C containing 5.0% by weight and linear polyester B containing less than 0.5% by weight of a flame-retardant element are laminated in the order of A / B / C in the thickness direction. A flame-retardant coating laminate characterized by being present. 2. The flame-retardant coating laminate according to claim 1, wherein the flame-retardant element is phosphorus or halogen. 3. The flame retardant according to claim 1 or 2, wherein the flame retardant element is copolymerized with linear polyesters A, C and B as a flame retardant composed of a phosphorus or halogen compound. Flammable coating laminate. 4. The linear polyesters A, C and B are linear polyesters containing an aromatic dicarboxylic acid as a main acid component and ethylene glycol as a main diol component. The flame-retardant coating laminate according to any one of claims. 5. The flame-retardant coating laminate according to claim 4, wherein the aromatic dicarboxylic acid of the linear polyesters A, C and B is terephthalic acid or 2,6-naphthalenedicarboxylic acid. 6. The flame-retardant element is contained as a flame-retardant comprising one or more compounds selected from the phosphorus compounds represented by the following chemical formulas 1, 2 and 3. The flame-retardant coating laminate according to claim 5. [Chemical 1] [Chemical 2] [Chemical 3] In the formula, R ₁ and R ₅ are the same or different groups and each represents a hydrocarbon group having 1 to 18 carbon atoms, R ₂ ,
R ₃ is the same or different group and represents a hydrocarbon group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms or a hydrogen atom, and A ₁ , A ₂
Represents a divalent or trivalent organic residue having 2 to 8 carbon atoms, R ₄ represents a carboxy group, a hydroxyl group or an ester thereof, R ₆ represents a carboxy group, a hydroxyl group or an ester thereof, or It represents a divalent ester-forming functional group that forms a ring with A ₂ via the group represented by 4. [Chemical 4] 7. A flame-retardant element is contained as a flame-retardant comprising one of a monoalkyl acid phosphate and a dialkyl acid phosphate represented by the following chemical formulas 5 and 6 alone or a mixture of both. The flame-retardant coating laminate according to any one of claims 1 to 5. [Chemical 5] [Chemical 6] (In the formula, R is an alkyl group having 1 to 8 carbon atoms) 8. The linear polyesters A and C contain 1.0 to 2.0% by weight of phosphorus element, and the linear polyester B contains less than 0.2% by weight of phosphorus element. The flame-retardant coating laminate according to any one of claims 1 to 6. 9. The thickness of the linear polyesters A and C is 0.01 to 3 times the thickness of the polyester B, and the thickness of the linear polyesters A and C is 0.5 to 200 μm. The flame-retardant coating laminate according to any one of claims 1 to 8. 10. The thickness of the linear polyesters A and C is 0.05 to 1 times the thickness of the polyester B, and the thickness of the linear polyesters A and C is 1 to 100 μm. Item 9. A flame-retardant coating laminate according to item 9.