FI72927B - FLERSKIKTIGT MATERIAL. - Google Patents

Description

Multilayer material 1 72927

The invention relates to the production of composite materials, more particularly to multilayer materials. The invention can be used to promote the manufacture of reusable design drawing elements for use in graphic work.

The proposed multilayer material is useful in the production of partial drawings and allows a large amount of drawing work to be replaced by cutting by combination. The use of the proposed multilayer material will increase the productivity of designers by 15-20%, reduce the time required for design and significantly improve the quality of the designs.

U.S. Pat. No. 376,512 discloses a multi-layered material comprising a polyethylene terephthalate substrate to which an adhesive coating has been applied and which is covered with a matt surface coating layer. This material is intended to draw a graphic pattern with a pencil or marker. The topsheet is a filler-containing hydrophilic poly-20 polymer compound. This material has good physical properties and drawing properties. However, due to the presence of a hydrophilic polymer in the top layer, dimensional stability cannot be guaranteed under varying temperature and humidity conditions.

25 Another prior art material (SU inventor certificate 265 855 "Method for the preparation of a mat-finished polyethylene terephthalate film", issued May 5, 1976) comprises a polyethylene terephthalate substrate to which a matt surface layer has been applied. The top layer is made of a filler-containing polyethylene terephthalate oligomer compound. This material has good physical properties, but the insufficient hardness of the top layer makes it difficult to use hard pencils and sharp-drawing instruments for graphic work, as these damage the matte top layer too much and thus the number of possible repairs is limited.

2,72927

Yet another prior art multilayer material (cf. GB Patent 1,061,784, issued March 15, 1967) comprises a polyethylene terephthalate substrate having an adhesive matte surface and a top layer applied thereto. This material has good physical properties and drawing properties. However, the method proposed for the preparation of this material and its composition are quite complicated and its further processing in order to obtain a multilayer material having adhesion properties is quite difficult.

A prior art multilayer material (cf. GB Patent 1,158,464, issued July 16, 1969) further comprises a paper layer having an outer protective layer, an adhesive coating and a protective layer applied thereto. This material has good drawing and adhesion properties. The poor strength properties, opacity and specific adhesion properties of this multilayer material prevent the multiple uses associated with mechanizing drawing work.

Still known in the art is a multilayer material comprising a polyethylene terephthalate substrate and a matte topsheet consisting of a filler-containing mixture of vinyl chloride / vinyl acetate and vinyl chloride / vinylidene chloride diethylene-olefinate-oleate-α inventor certificate 518 384, Cl. B32 B 27/36, issued December 30, 1974. The technology involved in the manufacture of this multilayer material is very simple.In addition to good drawing properties, it has good physical properties along with transparency and dimensional stability under varying climatic conditions. however, it is limited and, in particular, cannot be used to make reusable sub-drawings in graphic work, and due to the lack of adhesive properties, this prior art material 35 cannot be utilized in the design process. for mechanization, in particular for the introduction of new and advanced technology in the production of 3 72927 documents, such as the planar method. This method essentially involves the use of standard elements that can be attached and glued to the base sheet of the drawing, wherein the text elements are drawn on a laminated material having both drawing and adhesion properties. Thus, when making a design version, it is not necessary to redraw each version, but it is sufficient that the type elements drawn on the self-adhesive multilayer material 10 are moved according to the new plan and the drawing is completed with the necessary hyphens. The transfer of type elements made of self-adhesive laminate does not affect the integrity of the base sheet of the drawing on which the version designed for the base sheet is assembled.

The main object of the present invention was to provide a reusable multilayer material which combines self-adhesive and drawing properties, good physical properties, translucency in the ultraviolet and visible light spectral regions, and dimensional stability under varying air temperature and humidity conditions, and includes multilayer conditions. the paper layer.

The invention relates to a multilayer material comprising a transparent polyethylene terephthalate substrate, an adhesive coating applied to the reverse side of the poly-ethylene terephthalate substrate and a layer of tracing paper on the front side.

The invention is characterized in that the multilayer material further comprises a non-stick paper layer on top of the adhesive coating, the ratios of the components being 30% by weight as follows: simil paper 3-6 polyethylene terephthalate substrate 24-28 adhesive coating 4-5 a 30-50-4,72927% aqueous dispersion of a copolymer having a comonomer ratio of between 15: 84: 1 and 49: 49: 2, or a mixture containing a 30-50% aqueous dispersion of this copolymer and a butyl acrylate and vinyl a 30-50% aqueous dispersion of a copolymer of n-butyl ether with a comonomer ratio of between 4: 1 and 4: 2, the weight ratio between these dispersions being as follows: vinyl acetate / butyl acrylate / 10-50 acrylic acid copolymer % aqueous dispersion 50-80 butyl acrylate / vinyl-n-butyl of the 30-50% by weight aqueous dispersion of the ether copolymer The remaining adhesive coating composition according to the invention makes it possible to vary the adhesion of the multilayer material to the base drawing sheet within wide limits (0.7-3.5 Pa). The adhesion is high enough to prevent undesired self-migration of the multilayer material on the base drawing sheet in the graphic work process, and in addition, the opaque top layer of the base drawing sheet remains intact after removal of the multilayer material. At the same time, the adhesive coating composition ensures the integrity of the drawing as a whole when the self-adhesive multilayer material elements are finally bonded to the base drawing sheet by prolonged contact. The bonding effect results from the presence of components containing similar functional groups in the adhesive coating and the basic drawing material, and from the change of the polymer forming the adhesive coating from a viscous flow state to a highly elastic state. Prolonged contact between the two materials, i.e. the base material of the drawing and the multilayer material according to the invention, is guaranteed only when the copolymer dispersion contains 15-49% by weight of vinyl acetate responsible for the combining effect. Adequate adhesion between the adhesive coating and the polyethylene terephthalate substrate can be achieved with a butyl acrylate content as low as 20% by weight. The butyl acrylate content exceeding 84% by weight tends to degrade the adhesion properties of the multilayer material in a short contact time, thus affecting its re-use. A dry matter content of 30-50% by weight in the aqueous adhesive coating dispersion is sufficient for the adhesive coating in the thickness range of 4-6 μm. This guarantees the desired degree of adhesion to the basic drawing materials to which the multilayer material is applied in a detailed assembly drawing method.

A polyethylene terephthalate film is used as the substrate for the multilayer material according to the invention. Polyethylene terephthalate belongs to the group of polymeric esters having a straight-chain macromolecular structure. By stretching the polyethylene terephthalate film in the longitudinal and transverse directions, the polymer obtains a crystal structure which gives the film transparency, good physical properties and dimensional stability over a wide range of temperature and relative humidity conditions. The monolayer material according to the invention, which contains 24% by weight of polyethylene terephthalate substrate, has all the desired strength properties. Increasing the polyethylene terephthalate substrate content to more than 28% by weight significantly increases the cost of the multilayer material of the invention and thus does not make sense.

The plain paper layer consists either of a polymer blend containing a hydrolyzable component (cellulose triacetate) and a non-hydrolyzable component (a copolymer of terephthalate-diacid and diethylene glycol) or of a polyfunctional copolymer (vinyl acetate / vinyl chloride) containing both vinyl acetate / vinyl chloride -hydrolysable functional groups. A multilayer material having such a composition has a hydrophilic surface associated with adequate water resistance. The incorporation of aromatic inorganic pigments into the simili paper composition ensures reliable attachment of the graphic designs to the multilayer material. A 3% by weight carbonless paper content is sufficient for a multilayer material according to the invention having the desired optical, surface finishing and mechanical properties, while increasing the carbonless paper content above 6% by weight reduces the adhesion of the smooth paper layer and the polyethylene terephthalate substrate. iillä.

The non-stick paper layer is designed to protect the adhesive coating. It consists of a paper substrate made of a cellulosic material and a non-stick (paraffin, polyethylene or silicone) coating.

The text element designs are pre-printed on the multilayer material according to the invention using polygraphic or lithographic (offset, electrophotographic, etc.) methods.

When working with the detailed design version, the relevant models are cut off and, after removing the protective paper cover, placed on the drawing and lightly pressed into the desired position. After all the necessary text elements have been glued in place, the drawings are completed using pencils or ink pens.

The assembly of text elements made of the multilayer material according to the invention not only reduces the labor costs associated with the graphic work, but also considerably facilitates the detailed preparation of the design versions. In accordance with previous practice, each version 25 was drawn complete, with the average number of versions averaging 4. The use of the multilayer material of the invention saves the designer the hassle of redrawing each graphic element when working on a new version, as one graphic element in type 30 element can be replaced with another. and the only task remains to correct the hyphens.

Thus, the cost of detailed preparation of design versions is drastically reduced, 35 drafting work is simplified, the quality of designs is improved, and the time required to produce graphic documents is greatly reduced.

7,72927

The multilayer material according to the invention is prepared by successively applying a layer of carbon paper on one side and an adhesive coating on the other side to the polyethylene terephthalate substrate. The non-stick paper layer is rolled over the adhesive-5 coating.

The simil paper compound is prepared as follows:

The solvent mixture and the film-forming resin are placed in a blender equipped with a paddle mixer. After the resin has dissolved (takes about 4-5 hours), the pigments are added and mixed thoroughly. The resulting mixture is then passed through a ball mill where it takes 6 hours for the pigments to disperse.

The slurry thus obtained is filtered immediately before feeding to the coating machine.

The application of the simil paper compound to the polyethylene terephthalate substrate is performed by a continuous casting coating and drying machine. The simil paper material applicator comprises an extrusion nozzle and a cross shaft. The coating speed is 15-20 m / min. The drying of the simil paper layer 20 takes place with hot air in a drying tunnel. The air temperature in the drying tunnel is 50-60 ° C in zone I, 70-90 ° C in zone II and 100-120 ° C in zone III. The thickness of the dry simil paper layer is 5-7 pn.

The polyethylene terephthalate substrate / simil paper material multi-layer material is fed to a second coating and drying machine to apply an aqueous adhesive dispersion to the polyethylene terephthalate substrate on the opposite side of the simil paper layer.

The aqueous adhesive dispersion is prepared as follows: an aqueous dispersion of a copolymer of vinyl acetate, butyl acrylate and acrylic acid and an aqueous dispersion of a copolymer of butyl acrylate and vinyl n-butyl ether with vigorous stirring are placed in a vessel equipped with a stirrer in the required amounts.

The coating applicator comprises a dip roll and a press roll. The coating speed is 5-8 m / min. Drying is performed in a drying tunnel with air heated to 70-85 ° C. The thickness of the dry adhesive coating is 3-4 μm.

/

A cold calender is used to roll a non-stick pa-5 perlayer onto the adhesive coating.

The finished multilayer material is cut to the desired sizes and packed in packs of 50.

The multilayer material obtained above is tested to determine the following properties: adhesion to the drawing substrate, Pa, aging resistance, days, reusability, multiplier.

Adhesion to the drawing substrate is determined with a tensile testing device at a delamination rate of 50 mm / min.

15 Aging resistance is defined as the number of days during which the adhesive properties of a multilayer material are maintained.

Reusability is characterized by the number of times a multilayer piece of material on which a text-20 element is placed can be used while retaining all performance characteristics.

Example 1

The multilayer material contains the following percentages by weight: 1. Polyethylene terephthalate substrate 24 25 2. Simil paper layer containing 3% by weight: vinyl chloride / vinyl acetate copolymer 52 zinc oxide 36 silicon oxide-butyl oxide / acyl acylate 12 30 ratio is 15: 82: 1 35 4. The rest of the non-stick paper layer is 9,72927

The multilayer material is obtained as follows: On a 25 pn thick polyethylene terephthalate substrate, a simil paper compound having a composition by weight is applied: 5 vinyl chloride / vinyl acetate copolymer 15.0 zinc oxide 12.0 silica 4.0 ethyl acetate 30.0 10 butyl acetate

The simil paper compound is prepared as follows: 150 kg of ethyl acetate, 190 kg of butyl acetate and 75 kg of vinyl chloride / vinyl acetate copolymer are placed in a mixer equipped with a paddle mixer. After the copolymer resin has dissolved in the mixer, 60 kg of zinc oxide and 20 kg of silica are added. The contents of the mixer are mixed thoroughly and then passed to a ball mill where the dispersion process is continued for 6 hours. The slurry thus obtained is filtered immediately before being fed to the coating unit 20. The coating unit used to apply the carbon paper material to the polyethylene terephthalate substrate is a continuous cast coating and drying machine. The simil paper material applicator comprises an extrusion nozzle and a cross shaft. The dry paper layer is dried with hot air in a drying tunnel. The air temperatures in the drying tunnel are 70 ° C in zone I, 90 ° C in zone II and 120 ° C in zone III. The coating speed is 18 m / min. The thickness of the dry simil paper layer is 5 pn.

On the reverse side of the polyethylene terephthalate substrate, an adhesive compound having a composition by weight of: vinyl acetate / butyl acrylate / acrylic acid copolymer having a comonomer ratio of 84: 15: 1 is applied in an aqueous dispersion (dry weight of 35.8% by weight). 72927

The adhesive compound is prepared as follows: An aqueous dispersion of 25 kg of vinyl acetate / butyl acrylate / acrylic acid copolymer (comonomer ratio 15: 84: 1) is placed in a vessel equipped with a stirrer and 25 l of distilled water is added using a stirrer.

The finished adhesive dispersion is applied to the reverse side of the polyethylene terephthalate substrate by means of a dipping roller and a press roll. The coating speed is 6 m / min. The air temperature in the drying tunnel is 70 ° C. The thickness of the dry adhesive coating is 3 Jim. The cold calender is used to roll a non-stick paper layer consisting of a base paper with a basis weight of 80 g / m 2 and a 2 μm thick silicone coating. The properties of the resulting multilayer material are: adhesive strength, Pa 3.5 number of repeated adhesives to the drawing base 2

Example 2 20 The multilayer material contains in weight percent: 1. Polyethylene terephthalate substrate 28 2. Simil paper layer containing 6% by weight: cellulose triacetate 61 25 terephthalic acid / diethylene glycol copolymer 17 butylate copolymer with a comonomer ratio of 15: 84: 1 50 butyl acrylate / vinyl-n-butyl-35 ether copolymer with a comonomer ratio of 4: 1 50 4. The rest of the non-stick paper layer n 72927

The multilayer material is obtained as follows: A simil paper compound having the following weight percent composition is applied to a 36 μm thick polyethylene terephthalate substrate: 5 cellulose triacetate 10.0 terephthalic acid / diethylene glycol copolymer 3.0 titanium dioxide ethanol 2.7 8.0

The method used to prepare and apply the simil paper compound is similar to that described in Example 1.

The tracing paper layer is dried at a temperature of: 50 ° C in zone I, 70 ° C in zone II and 100 ° C in zone III. The thickness of the simil paper layer is 7 μm.

On the reverse side of the polyethylene terephthalate substrate, an adhesive compound having a composition of 20% by weight of an aqueous dispersion of a vinyl acetate / butyl acrylate / acrylic acid copolymer having a comonomer ratio of 25: 84: 1 vinyl acetate / butyl) of the copolymer (38% by weight dry matter) is applied. - an aqueous dispersion of an ether copolymer with a comonomer ratio of the copolymer of 4: 1 (dry matter content 38% by weight) 25 30 distilled water 50

The method used to prepare and apply the adhesive compound is as described in Example 1.

The adhesive coating is dried at 75 ° C and a paraffin-coated non-stick paper layer is rolled on it.

2

The paper has a basis weight of 95 g / m 2 and a paraffin coating thickness of 12,72927 is 8 μm. The properties of the multilayer material thus obtained are: adhesion strength, Pa 1.2 number of repetitive glues-5 to the drawing base 10

Example 3

The multilayer material contains in weight percent: 1. Polyethylene terephthalate substrate 26 2. Simil paper layer containing 4 to 10 weight percent: vinyl chloride / vinyl acetate mixed polymer 52 zinc oxide 36 silica oxyacylate / acyl ethyl acetate / 4.5% with a comonomer ratio of 15: 84: 1 80 20 butyl acrylate / vinyl-n-butyl ether copolymer with a comonomer ratio of 4: 1 20 4. The rest of the non-stick paper layer

The methods used to prepare the multilayer material are similar to those described in Example 1. 25 The properties of the multilayer material are: adhesive strength, Pa 2.0 number of repeated adhesives on the drawing base up to 15 Example 4 30 The multilayer material comprises in weight percent: 1. Polyethylene terephthalate substrate 27 2. Simil paper coating layer containing Adhesive coating containing 5% by weight of: vinyl acetate / butyl acrylate / acrylic acid copolymer with a comonomer ratio of 49: 49: 2 4. The rest of the non-stick paper layer

The methods used to prepare this multilayer material are similar to those described in Example 1.

10 The properties of the multilayer material thus prepared are: adhesive strength, Pa 0.7 number of repeated glues to the drawing base low adhesion 15 Example 5

The multilayer material comprises in weight percent: 1. Polyethylene terephthalate substrate 25 2. Simil paper coating layer containing in weight percent: 5 20 cellulose triacetate 61 terephthalic acid / diethylene glycol mixed polymer 4-titanium dioxide with a comonomer ratio of 49: 49: 2 50 30 butyl acrylate / vinyl-n-butyl ether copolymer with a comonomer ratio of 4: 1 50 4. The rest of the non-stick paper layer

The methods used to prepare this multilayer material are similar to those described in Example 1.

14 72927 The properties of the multilayer material thus prepared are: adhesive strength, Pa 1.0 number of repeated adhesives-5 to the drawing substrate 15

Example 6

The multilayer material comprises, by weight: 1. Polyethylene terephthalate substrate 28 2. Simil paper coating layer containing 6% by weight: cellulose triacetate 61 terephthalic acid / diethylene glycol copolymer 5 The -20 isomer ratio is 49: 49: 2 80 butyl acrylate / vinyl n-butyl ether copolymer with a comonomer ratio of 4: 1 20 4. The rest of the non-stick paper layer

The methods used to prepare this multilayer material are similar to those described in Example 1.

The properties of the multilayer material thus prepared are: adhesive strength, Pa 1.5 number of repeated adhesives to the drawing substrate up to 15

Table 1 brings the adhesion strength values and the numbers of multilayer materials of the invention into the drawing substrate relative to the adhesive coating compositions. 35 15 72927

table 1

Es; Lm> Composition of adhesive dispersion_Performances_No. Vinyl-Butyl-Vinyl-Adhee- Lithium / butyl / vinyl / butylity of repetitive acetate-acrylate-acetate liquors 5-acrylic-n-bu - number of lacrylates per plate / acyl ether / acrylic-drawing-rylic acid-teracid-co-acid-mixed base copolymer polymer polymer iter aqueous aqueous dispersion dispersion, sio, como ratio buty - 10 comonomer-ester-acrylate ratio by weight w / w as a percentage of the n-butyl ether-copolymer dispersion, wt% 15 1 15: 84: 1 - - 3.5 2 2 15: 84: 1 4: 1 50:50 1,2 10 3 15: 84: 1 4: 1 80:20 2.0 over 15 4 49: 49: 2 - - 0.7 low adhesion 5 49:49 : 2 4: 1 50:50 1.0 15 20 6 49: 49: 2 4: 1 80:20 1.5 over 15

Table 2 compares the performance properties of the multilayer materials according to the invention with the performance properties of a material belonging to the prior art.

25

Table 2

Performance Known according to Example 1 Properties according to Example 2 material new multi-layer new multi-layer material layer material 30 tensile strength, MPa 160-170 150-160 150-160 number of folds with folding machine more than 1000 more than 1000 more than 1000 aging resistance, days - 300-400 300-400 adhesion to the film substrate, Pa - 3.5 1.2 reusability »times“ 2 10 16 72927

The numerical values shown in Table 2 mean that the new multilayer material has fully retained the physical properties of the known material, while also gaining adhesion properties, thus allowing it to be reused to meet the needs of mechanized graphic work.

Claims (1)

A multilayer material comprising a transparent polyethylene terephthalate substrate, an adhesive coating applied to the reverse side of a polyethylene terephthalate substrate and a layer of plain paper on the front side, characterized in that it further comprises 3 -6 polyethylene terephthalate substrate 24 to 28 adhesive coating 4-5 non-stick paper layer the rest and the adhesive coating consists of a 49-50% aqueous dispersion of either a vinyl acetate, butyl-15 acrylate and a copolymer of acrylic acid with a comonomer ratio of: : 49: 2, or a mixture containing a 30-50% aqueous dispersion of this copolymer and a 30-50% aqueous dispersion of a copolymer of butyl acrylate and vinyl n-butyl ether having a comonomer ratio of between 4: 1 and 4: 2, wherein disperside of these The ratio by weight of n is as follows: 30-50% by weight aqueous dispersion of vinyl acetate / butyl acrylate / 25 acrylic acid copolymer 50-80% by weight aqueous dispersion of butyl acrylate / vinyl n-butyl ether copolymer