JPH07101024A - Receptive sheet for flame-retardant printing - Google Patents

Abstract

(57) [Summary] [Structure] On at least one side of a plastic film, a poly (meth) acrylic acid ester copolymer containing a reactive monomer, and a polymer binder containing a cationic polymer as a main component, Oil absorption is 200-400ml / 100g
And a resin layer of a poly (meth) acrylic acid ester copolymer containing the reactive monomer having a resin hydroxyl value of 40 or more. The linear polyesters A and C containing 0.5 to 5.0% by weight of the flame retardant element and the linear polyester B containing less than 0.5% by weight of the flame retardant element are A / B / C in the order of thickness. A flame-retardant receiving sheet for printing, which is a laminated polyester film. [Effect] UL-94 has excellent printing characteristics and high flame retardancy while maintaining the high heat resistance, hydrolysis resistance, mechanical properties, chemical resistance, etc. of ordinary polyester films. The present invention provides a printing receiving sheet that sufficiently achieves the VTM-2 rank.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing receiving sheet and is applied to various printing sheets such as offset printing. More particularly, it relates to a printing receiving sheet having excellent printability, ink setting property, ink drying property, ink adhesion property and water resistance. More specifically, while maintaining the characteristics of polyester, US Underwriters Laboratories (UNDERWRITERS L
The present invention relates to a flame-retardant printing receiving sheet having a flame retardancy level equivalent to VTM-2 defined in UL-94 of ABORATORIES).

In particular, the present invention provides a flame-retardant printing receiving sheet having high flame retardancy suitable for applications such as caution labels for home electric appliances and vending machines and process control labels requiring flame retardancy.

[0003]

2. Description of the Related Art In a printing receiving sheet, a paper support has been dominant in the past, but in recent years, a plastic film has begun to be used as a support. Among plastic films, polyester films having excellent properties such as mechanical properties and transparency are becoming popular. However, in general, the surface of the polyester film has high cohesiveness and poor adhesiveness, and therefore, when various printing treatments are performed on the surface, the adhesiveness to the ink is made to be strong, and therefore the affinity to the ink is excellent. The formation of the coating layer is actively practiced. As such a printing receiving sheet, a printing receiving sheet in which a coating layer made of an aqueous polymer resin containing a white pigment is provided on the surface of a polyester film, for example, JP-A-57-82085 is known. There is.

Recently, there has been known a printing receiving sheet provided with a coating layer containing a polymer binder such as an acrylic resin and inorganic or organic particles.

[0005]

However, when an aqueous polymer resin is used, such a receiving sheet for printing is
Since the water resistance and hot water resistance of the coating layer are poor, deformation such as dissolution and expansion of the coating layer may occur under high temperature or high humidity atmosphere, or the adhesive strength of the coating layer may decrease significantly when subjected to hot water treatment. Become.

Further, the one provided with a coating layer containing a polymer binder such as an acrylic resin and inorganic or organic particles,
Since the ink absorption amount of the coating layer is relatively low, the printability such as ink setting property and ink drying property is poor, and the appearance of the coating layer is improved by using a polymer binder having a poor affinity with inorganic or organic particles. It will be extremely bad. Further, the flame retardance is insufficient, and there remains a problem in the above-mentioned applications requiring high flame retardancy.

It is an object of the present invention to provide a printing receiving sheet which has alleviated the above problems, has good printing characteristics, and has high flame retardancy.

[0008]

In order to achieve the above object, the present invention provides a poly (meth) acrylic acid ester copolymer containing a reactive monomer on at least one side of a plastic film, and a cationic system. Polymer binder mainly composed of polymer and oil absorption of 200 to 400 m
1/100 g of porous particles, further comprising a coating layer having a coating layer in which the resin hydroxyl value of the poly (meth) acrylic acid ester copolymer containing the reactive monomer is 40 or more, A plastic film contains linear polyesters A and C containing 0.5 to 5.0% by weight of a flame retardant element and a linear polyester B containing less than 0.5% by weight of a flame retardant element in the thickness direction of A / B / A gist of the flame-retardant printing receiving sheet is a polyester film laminated in the order of C.

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 other 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.

[0015]

[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.

[0016]

[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 are (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.

Among these compounds, the compound of Chemical formula 8 is particularly preferable because it has a good copolymerization reactivity with the polyester and is less scattered 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.

[0020]

[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.

[0021]

[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 a compound containing a flame retardant element to polyester is not particularly limited. For example, JP-A-51-82392 and JP-A-2-5382 are known.
1, JP-A-63-133589, JP-A-62-2774
It can be carried out by a conventional polymerization method disclosed in Japanese Patent Publication No. 29, etc.

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.

In the polyester film of the present invention, a linear linear polyester A, a linear polyester B, and a linear polyester C are laminated A / B / C in the thickness direction. In case of flame retardant UL-94,
Required for VTM-2 compliance. A / B, B
The flame retardancy level is lowered in the structures such as / A / C, A / C / B, 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.

A method of laminating the linear polyesters A, B and C may be 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. 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 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 according to 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 film A and / or C which is in contact with the coating layer in order to more adhere the linear polyester film A and / or C to the coating layer impairs 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 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.

In the present invention, the polymeric binder is mainly composed of a poly (meth) acrylic acid ester copolymer containing a reactive monomer and a cationic polymer. The main component in the present invention means that it 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.

The poly (meth) acrylic acid ester copolymer referred to in the present invention is a poly (meth) acrylic acid ester copolymer containing a reactive monomer. As such a reactive monomer, known ones can be selected and used. For example, those having a carboxyl group such as acrylic acid, methacrylic acid, itaconic acid, carboxyethyl acrylate, carboxyphenyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, Those having a hydroxyl group such as 2-hydroxyethyl methacrylate, 3-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate,
Acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-ethylacrylamide, N, N-
Those having an amide group such as dimethyl acrylamide, N-methylol acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, N, N-diethyl methacrylamide, N-methylol methacrylamide, glycidyl acrylate, glycidyl methacrylate, etc. Having a glycidyl group, 7-amino-3,7-dimethyloctyl acrylate, 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate, 7-amino-3,7-dimethyloctyl methacrylate, 2-dimethylaminoethyl methacrylate And those having an amino group such as 2-diethylaminoethyl methacrylate. Examples of the monomer unit of the poly (meth) acrylic acid ester copolymer in the present invention include methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, methyl methacrylate, ethyl. Methacrylate,
Examples thereof include butyl methacrylate, propyl methacrylate, mepentyl tacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate and the like.

The resin hydroxyl value defined in the present invention is defined as follows. That is, it is the number of mg of potassium hydroxide corresponding to the number of moles of hydroxyl groups contained in 1 g of the sample resin. In the present invention, the resin hydroxyl value is calculated and determined from the hydroxyl group of the monomer charged in the polymerization process of the poly (meth) acrylic acid ester containing the reactive monomer.

The resin hydroxyl value of the poly (meth) acrylic acid ester containing the reactive monomer used in the present invention must be 40 or more. Resin hydroxyl value is 40
When it is less than 40, the affinity with the porous particles is poor and the adhesion to the substrate and the appearance of the coating film are likely to deteriorate, so that it is preferably 40 or more, more preferably 50 or more.

A polymer electrolyte is usually added to the polymer binder in the present invention in order to adjust the electric resistance of the coating layer. In the present invention, as the polymer electrolyte, a cationic polymer such as a quaternary ammonium salt polymer is preferably used from the viewpoint of conductivity and compatibility with the polymer binder. The quaternary ammonium salt polymer is a polymer having at least one quaternary ammonium salt in the repeating unit chain, and examples thereof include poly (2-hydroxy-3-methacryloxypropyltrimethylammonium chloride) and poly ( 2-hydroxy-3-methacrylopropyltriethylammonium chloride), poly (2-hydroxy-2-acryloxypropyltrimethylammonium chloride), poly (2-hydroxy-3-acryloxypropyltriethylammonium chloride),
Poly (2-methacryloxyethyltrimethylammonium chloride), poly (2-methacryloxyethyltriethylammonium chloride), poly (2-acryloxyethyltrimethylammonium chloride), poly (2-acryloxyethyltriethylammonium chloride), poly ( Vinylbenzyltrimethylammonium chloride), poly (vinylbenzyltriethylammonium chloride), poly (4-vinylN-methylpyridinium chloride), N, N-dimethyl-substituted-3,5-
Methylpiperidinium chloride resin, poly (dimethyldiallylammonium chloride), poly (diethyldiallylammonium chloride), polyethyleneimine hydrochloride, etc.
960), polymers of various quaternary ammonium salts and pyridinium salts, but other known polymers having various quaternary ammonium salts can be used.

The quaternary ammonium salt polymer may be used alone or in a mixture of two or more kinds. Furthermore, the fourth
It may be a copolymer of a quaternary ammonium salt and styrene or an acrylic acid ester. The acrylic acid ester as used herein means an acrylic acid ester or a methacrylic acid ester, and examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, Examples include propyl methacrylate and 2-hydroxyethyl methacrylate.

Specific examples of the quaternary ammonium salt polymer used in the present invention include, for example, Elekondo (Soken Kagaku), Chemistat (Sanyo Kasei), Colcoat (Colcoat), SAT-5 (Nippon Pure Chemical). , Dow ECR (Dow Chemical) and the like.

The porous particle in the present invention is a porous particle having pores on the surface of the particle, and can be freely filled and released with a liquid, a solid or a gas inside as a hollow porous or non-hollow porous form. Those are preferable from the viewpoint of ink absorbency.

The constituents of the porous particles include amorphous silica, anhydrous silica, aluminum silicate, magnesium silicate, zinc silicate, calcium silicate, hydrotalcite, zeolite, satin white, titanium oxide, and oxide. Aluminum, magnesium oxide, calcium carbonate, calcium sulfate, barium sulfate, diatomaceous earth, kaolin, talc, acid clay, activated clay, bentonite, ion exchange resin powder, urea resin powder, polyethylene resin powder, urea formalin resin powder, acrylic resin Powder, styrene-acrylic resin powder, etc. are mentioned.

The oil absorption of these porous particles is 2
It is necessary to be 100 to 400 ml / 100 g.
If the oil absorption is less than 200 ml / 100 g, the oil-based offset ink absorbency of the resulting sheet for electrical decoration is poor,
The ink cannot be set sufficiently and the ink cannot be dried sufficiently.
When the amount exceeds 0 ml / 100 g, the obtained printed matter becomes light and the so-called sunken printed matter is apt to occur.

The average particle diameter of the porous particles used in the present invention is 0.1 μm to 25 μm, preferably 0.5 μm to 10 μm.
From the viewpoints of handleability, coatability, printability, etc.,

The content of the porous particles in the receiving layer is preferably 20 to 100 parts by weight, more preferably 30 to 70 parts by weight, based on 100 parts by weight of the polyolefin resin / polymer binder. is there. If the content is less than 20 parts by weight, the ink setting property and the ink drying property become insufficient, and 1
If it exceeds 100 parts by weight, the adhesiveness between the receptor layer and the film support tends to deteriorate.

The smoothness of the coating layer constituting the printing receiving sheet of the present invention is preferably 2 to 5000 seconds, more preferably 10 to 3000 seconds. When the smoothness is smaller than the range of the present invention, the ink permeation rate is too high and the printed matter becomes pale, which is not preferable. Further, when it is larger than the range of the present invention, the ink permeation rate is too low and the ink is likely to remain on the coating layer surface, and when the printing surface is rubbed,
It is not preferable because the printed surface is easily stained with residual ink.

Further, the thickness of the coating layer constituting the printing receiving sheet of the present invention is not particularly limited,
The thickness is preferably 0.5 to 50 μm, and is preferably in the range of 1.0 to 20 μm from the viewpoint of uniform forming property of the coating layer and adhesion. Further, the coating layer may optionally contain known additives within a range that does not impair the characteristics of the present invention, for example, a coating property improver, a thickener, an antioxidant, an ultraviolet absorber, a dye and the like. Good.

The setting time of the oil-based offset ink of the printing sheet of the present invention is preferably within 30 minutes, more preferably within 20 minutes. Ink set time is 30
If it is more than a minute, not only will the ink drying time be delayed,
Problems such as set-off occur during printing. Here, the set time of the oil-based offset ink is a value obtained based on the following measuring method. That is, a printability tester RI-2 type (manufactured by Akira MFG.
Set 4-division rolls of m and width of 4.7 cm, apply 0.3 cc of oil-based offset printing ink "TK Mark Five New" Beni (Toyo Ink Co., Ltd.) to each roll with an ink pipettor, and print solidly. Do. Next, OK coated paper (Oji Paper Co., Ltd.)
Product) and the line pressure of 353 g /
This is to observe the time required for running a metal roll of cm to stop the transfer to the OK coated paper.

In the present invention, as a method for providing a coating layer, a film support which is a base material is stretched in advance in a film forming step, then a liquid adjusted to a predetermined amount is applied, and then dried. A method of providing a coating-drying step after winding as a base film single film is preferably applied.

The coating method is not particularly limited, but since it is possible to perform thin film coating at high speed, known methods such as gravure coating method, reverse coating method, reverse gravure coating method, kiss coating method, die coating method and bar coating method are known. The method can be applied. Although the coating speed and the coating film drying conditions are not particularly limited, it is desirable that the coating film drying conditions be within a range that does not adversely affect various properties of the coating layer and the support.

[0049]

[Characteristic Measuring Method] First, various characteristic measuring methods in the present invention will be described.

(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) Surface Roughness According to JIS B0601-1967, a cutoff of 0.
Center line average roughness Ra (μ
m) and the maximum roughness Rt (μm).

(3) Oil Absorption of Porous Particles The oil absorption was measured according to JIS K-5101 to obtain the oil absorption (ml / 100 g) corresponding to 100 g of particles.

(4) Adhesiveness of coating layer The adhesiveness of the coating layer / support is such that a crosscut (100 pieces / 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%) ×: Poor (peeling area 20% or more)

(5) Water resistance of coating layer A cotton swab was dipped in water, and the coating layer was slightly rubbed for evaluation. The criteria are as follows.

⊚: Very good (no peeling at all) ○: Good (peeling after rubbing 10 to 15 times) Δ: Slightly inferior (peeling after rubbing 5 to 9 times) ×: Poor (peeling after less than 5 times)

(6) Coating layer thickness It was determined by measuring with a micrometer or a dial gauge.

(7) Ink setting property The following evaluation criteria were applied by the evaluation method described above.

◎: Less than 30 minutes ○: 30 minutes or more and less than 45 minutes △: 45 minutes or more and less than 60 minutes ×: 60 minutes or more

(8) Ink drying time Printing was carried out in the same manner as in the ink setting property measurement, and O was printed on the printing surface.
The coated surfaces of the K-coated paper were overlaid, allowed to stand for 24 hours in that state, and the printed surface was rubbed with a light nail to evaluate. The criteria are as follows.

◯: No peeling Δ: Peeling after repeated rubbing ×: Peeling easily

(9) Electrophotographic copying and recording property Full color electrostatic copying machine PIXEL D manufactured by Canon Inc.
A full color test pattern was printed using io, the printing quality and running property were evaluated, and the recording property was judged according to the following criteria.

◎: Very good ○: Good Δ: Slightly inferior ×: Poor

(10) Flame Retardant US Underwriters Laboratories (UNDARW
U of WRITER LABORATORIES standard
It evaluated according to L-94.

[0065]

EXAMPLES Next, the present invention will be specifically described by way of examples. In addition, all compounding parts in the examples are parts by weight.

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 was used.
A coating layer having the following composition was applied to the layer surface by a gravure coater (the coating amount of the coating layer after drying was 5 μm).

[Coating layer] 38 parts by weight of toluene and 1 part of isobutanol were placed in a flask equipped with a condenser, a thermometer and a stirrer.
0.5 parts by weight, 2-hydroxyethyl methacrylate 7
Parts by weight, 10 parts by weight of n-butyl methacrylate, 1 part by weight of acrylamide, 28 parts by weight of methyl methacrylate,
Acrylic acid 0.3 parts by weight and azobisisobutyronitrile 0.5 parts by weight were charged, stirring polymerization was completed at 80 ° C. for 2 hours, and a poly (meth) acrylic acid ester copolymer having a resin hydroxyl value of 64 was obtained. Obtained. 70 parts by weight of a poly (meth) acrylic acid ester copolymer containing this reactive monomer,
30 parts by weight of cationic polymer "Elecond" (manufactured by Soken Kagaku), 1 part by weight of flame retardant ("CR-509" manufactured by Daihachi Chemical), and "fine seal" as porous particles (manufactured by Tokuyama Soda)
Average particle diameter 3.5 μm Oil absorption 260 ml / 100 g)
40 parts by weight of toluene / MEK mixed solvent (1/1)
A coating solution diluted to 5% by weight was obtained.

The printing receiving sheet thus obtained is shown in Table 1.
As shown in (3), it is excellent in water resistance, adhesiveness, ink setting property, ink drying property, electrophotographic copy recording property and coating film appearance, and has flame retardancy of rank VTM-2.

Example 2 The phosphorus elements of the polyester used in Example 1 were changed to A and C.
A printing receiving sheet of the present invention was obtained in the same manner as in Example 1 except that 2.0% by weight of B and 0.4% by weight of B were added.

The characteristics of the obtained printing receiving sheet are, as shown in Table 1, excellent in water resistance, adhesiveness, ink setting property, ink drying property, electrophotographic copy recording property and coating film appearance.
The flame retardancy also has 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, the same coating agent as in Example 1 was used on the surface of the obtained polyester film on which the acrylic group-grafted hydrophilic group-containing polyester resin was undercoated to obtain the printing receiving sheet of the present invention in the same manner as in Example 1. It was

The properties of the printing receiving sheet thus obtained are, as shown in Table 1, excellent in water resistance, adhesiveness, ink setting property, ink drying property, electrophotographic copy recording property and coating film appearance.
The flame retardancy also has 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 printing characteristics were poor. If the coating layer is not applied in this way, it is not possible to obtain a print having excellent printing characteristics.

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 linear polyester A and C layers.

Next, A of the obtained polyester film was used.
A receiving sheet for printing was obtained in the same manner as in Example 1 by using the same coating agent as in Example 1 on the layer surface.

The characteristics of this printing receiving sheet are excellent as shown in Table 1, but the VT was found in the flame retardancy test.
It was lower than the M-2 standard, and high flame retardancy could not be obtained.

[0079]

[Table 1]

[0080]

INDUSTRIAL APPLICABILITY The present invention has good printing characteristics and high flame retardancy by applying a specific plastic film in a printing receiving sheet obtained by laminating a specific coating layer on at least one side of a plastic film. It was possible to obtain a printing receiving sheet having

Since the printing receiving sheet of the present invention thus obtained has excellent properties, it is particularly suitable for applications such as caution labels for home electric appliances and vending machines and process control labels requiring flame retardancy. Flammability can be imparted, UL-9
At 4, the VTM-2 rank can be fully achieved.

Claims (10)

[Claims] 1. A polymer binder containing a poly (meth) acrylic acid ester copolymer containing a reactive monomer and a cationic polymer as main components, and an oil absorption of 200 on at least one side of a plastic film. ~ 400ml / 1
In a printing receiving sheet having a coating layer containing 100 g of porous particles and further having a resin hydroxyl value of the poly (meth) acrylic acid ester copolymer containing the reactive monomer of 40 or more, the plastic film Is a linear polyester A containing 0.5 to 5.0% by weight of a flame retardant element,
Receiving sheet for flame-retardant printing, which is a polyester film in which C 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. . 2. The receiving sheet for flame-retardant printing 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. Receptive sheet for flammable printing. 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 printing receiving sheet according to any one of claims. 5. The flame-retardant printing receiving sheet 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 printing receiving sheet 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 printing receiving sheet 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 printing receiving sheet 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 linear polyester B, and the thickness of the linear polyesters A and C is 0.5 to 200 μm. The flame-retardant printing receiving sheet 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 linear polyester B, and the thickness of the linear polyesters A and C is 1 to 100 μm. The flame-retardant printing receiving sheet according to claim 9.