CN109760396A - Terylene advertising cloth and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of terylene advertising cloths and preparation method thereof, the preparation method comprises the following steps: modified polyester industrial yarns, which are carried out warping, weaving and calender lamination PVC film, is made terylene advertising cloth；Modified polyester industrial yarns are by the way that modified poly ester melt is carried out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oils, stretch, made from thermal finalization and winding；Modified poly ester the preparation method comprises the following steps: terephthalic acid (TPA), ethylene glycol, the binary acid with tert-butyl side group and 2,5,6,6- tetramethyl -2,5- heptandiol successively to be carried out to esterification and polycondensation reaction after mixing before solid phase polycondensation viscosifies.The warp tensile strength that product is made is >=110N/cm, and weft tensile strength is >=110N/cm, tearing strength >=35N/cm, peel strength >=10N/cm.Preparation method of the invention, simple process and low cost；Product obtained, peel strength is high, and application prospect is good.

Description

Terylene advertising cloth and preparation method thereof

Technical field

The invention belongs to polyester fiber technical field, it is related to a kind of terylene advertising cloth and preparation method thereof.

Background technique

With being constantly progressive for society and becoming increasingly abundant for commodity, advertising is quickly grown, and also proposed to advertising media Higher requirement.In recent years the flexible lamp house cloth occurred, gradually instead of once in advertising media prevailing neon light, The hard materials such as plastic cement film and organic glass, become the preferred material for lamp box of preparing advertising.The advantages of flexible lamp house cloth, shows The color glow of made lamp box, service life length, convenient transportation, using safe, light transmission Sticky Note can be both pasted on lamp box, It can also carry out the processing such as thermal transfer, superthermal print and computer description；Lamp box shape and size facilitate customization；Compare other materials at night Made lamp box is more eye-catching.Just due to this, though lamp house cloth developing history is shorter, rapidly sent out in production and application Exhibition.The warp-knitted bi-axial fabric being process by biaxial warp knitting machine is due to good mechanical property, simple process, process are short, speed The features such as fast and at low cost, the scrim material as flexible lamp box has obtained a large amount of uses.

Terylene is due to breaking strength is high, extension is good, dry and wet intensity difference is little, is unlikely to deform, wearability The feature that energy is good, light fastness is strong, percent thermal shrinkage is low, thermal stability is strong, long service life and durability are good, becomes advertising cloth Ideal material.But the flame retardant property of terylene is bad, although also there is flame-resistant terylene in the market, its higher cost, it is difficult to extensive As lamp house cloth.

Therefore, select a kind of suitable material be bonded with polyester material the performance that can improve lamp house cloth and at This.PVC commonly synthesizes high molecular material as one kind, cheap, from a wealth of sources, due to containing halogen atom on main chain, With excellent flame retardant property.PVC has high intensity, insulating properties, good resistance to climate variability and excellent geometry simultaneously Stability also has very strong resistance to oxidant, reducing agent and strong acid.PVC is a kind of suitable composite material.Pass through calendering It can be effectively compound by two kinds of materials.Since synthetic fibers (polyester industrial yarn) end is rare, surface is smooth and chemical activity is low, More difficult to establish adhesive bond at interface, the viscosity for enhancing polyester fiber and PVC generally need to be in PET fiber surface spreading polyurethane Class adhesive, polyurethane binding contains can be with the conjunction of fibre end base junction such as-NH₂,-OH ,-COOH isoreactivity group, can Enhance the binding strength of polyester fiber and PVC.

But polyester fiber finished product is the supramolecular structure of partially crystallizable, and crystalline portion strand is parallel to each other, and is in mostly Anti conformation, and amorphous region is then in cisoid conformation more, molecules align is quite close, the active group in polyurethane binding Group is difficult to penetrate into fibrous inside in turn in conjunction with the end group of fibrous inside, this largely affects polyester fiber and PVC Between adhesive effect power, affect the peel strength of terylene lamp house cloth (terylene advertising cloth).

Therefore, it studies between a kind of enhancing polyester fiber and PVC active force and then to prepare a kind of terylene that peel strength is good wide Accuse the great realistic meaning of cloth.

Summary of the invention

The purpose of the present invention is overcoming defect existing in the prior art, provides and make between a kind of enhancing polyester fiber and PVC Method firmly, and then a kind of terylene advertising cloth and preparation method thereof that peel strength is good is provided.The present invention is by the polyester It introduces 2,5,6,6- tetramethyl -2,5- heptandiols and the binary acid with tert-butyl side group is modified polyester, so that polyester Space free volume increases, and then makes the molecule reactive group such as-NH in the adhesion promoter of PVC₂,-OH ,-COOH etc. is in warm It is diffused into fiber gap in treatment process, obtains good interface and combine, thus improved viscous between fiber and PVC film Cooperation is used, so that the raising that the acquisitions such as peel strength, tearing strength are certain.

In order to achieve the above object, the present invention adopts the following technical scheme that:

Modified polyester industrial yarns are carried out warping, weaving and calender lamination PVC film and are made by the preparation method of terylene advertising cloth Terylene advertising cloth, the preparation method and the prior art of terylene advertising cloth of the invention are essentially identical, and most important difference is work The material of industry silk, the material of prior art terylene advertising cloth is conventional polyester, and the material of terylene advertising cloth of the invention is to change Property polyester；

The modified polyester industrial yarns are by the way that modified poly ester melt is carried out solid phase polycondensation thickening, melting, metering, is squeezed Out, it cools down, oil, stretching, made from thermal finalization and winding；

Modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, band tert-butyl side before the solid phase polycondensation viscosifies The binary acid and 2,5,6,6- tetramethyl -2,5- heptandiol of base successively carry out esterification and polycondensation reaction after mixing；

Binary acid with tert-butyl side group is 5- tert-butyl -1,3- phthalic acid, the own dioctyl phthalate of 2- tert-butyl -1,6-, 3- The own dioctyl phthalate of tert-butyl -1,6- or 2, the own dioctyl phthalate of 5- di-t-butyl -1,6-, the knot of 2,5,6,6- tetramethyl -2,5- heptandiols Structure formula is as follows:

The present invention changes polyester using 2,5,6,6- tetramethyl -2,5- heptandiol and the binary acid with tert-butyl side group Property, 2,5,6,6- tetramethyl -2,5- heptandiols and the binary acid with tert-butyl side group can significantly increase the space of modified poly ester The presence of tert-butyl in free volume, especially 2,5,6,6- tetramethyl -2,5- heptandiols and binary acid with tert-butyl side group It can cause the variation of main chain activity, to change the interaction force between chain element, the distance between molecule chain element also can Corresponding change occurs, increases modified poly ester cavity free volume.The increase of empty free volume makes in the adhesion promoter of PVC Molecule reactive group such as-NH₂,-OH ,-COOH etc. diffused into fiber gap during heat treatment, obtain good boundary Face combines, thus improve the adhesive effect between fiber and PVC film, so that the acquisitions such as peel strength, tearing strength are certain It improves.

As a preferred technical scheme:

The preparation method of terylene advertising cloth as described above, the synthesis step of described 2,5,6,6- tetramethyl -2,5- heptandiols It is rapid as follows:

(1) by 1~1.2:1:1.2~1.3:2.0~3.0 molar ratio by KOH powder, 3- methyl -3- hydroxyl butine, 3, 3- dimethyl-2-butanone and isopropyl ether mixing, react 2~4h under condition of ice bath, carry out crystallisation by cooling, centrifugation after reaction Separate, wash, refine and be dried to obtain octyne glycol；

(2) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2~3:10:0.01~0.03,40~50 DEG C temperature under the conditions of react 50~60min, be continually fed into hydrogen in reaction process, separated and purified after reaction To 2,5,6,6- tetramethyl -2,5- heptandiol.

The preparation method of terylene advertising cloth as described above, the own dioctyl phthalate of the 2- tert-butyl -1,6-, tert-butyl -1 3-, The synthetic method of the own dioctyl phthalate of 6- and the own dioctyl phthalate of 2,5- di-t-butyl -1,6- are as follows:

Wolframic acid and hydrogen peroxide are mixed first, 10~15min is stirred at room temperature, be then added raw alcohol first 80~ 1~2h is reacted under the conditions of 85 DEG C of temperature, then is warming up to 90~95 DEG C of 2~3h of reaction, and in reaction process, reactant is in always Reflux state finally carries out crystallisation by cooling, washing and purification；

When reaction starts, the molar ratio of wolframic acid, raw alcohol and hydrogen peroxide is 1:30~40:120~150；

The own dioctyl phthalate of the 2- tert-butyl -1,6-, the own dioctyl phthalate of 3- tert-butyl -1,6- and 2,5- di-t-butyl -1,6- oneself The corresponding raw alcohol of dioctyl phthalate is respectively 2- tert. butyl cyclohexanol, the pure and mild 2,4- di-t-butyl cyclohexanol of 4- t-butylcyclohexyl.

The preparation method of terylene advertising cloth as described above, the solid phase polycondensation viscosify the preparation step of preceding modified poly ester such as Under:

(1) esterification；

Terephthalic acid (TPA), ethylene glycol, the binary acid with tert-butyl side group and 2,5,6,6- tetramethyl -2,5- heptandiol are matched At slurry, catalyst, delustering agent and stabilizer is added after mixing, pressurization carries out esterification, pressurization in nitrogen atmosphere Pressure is normal pressure~0.3MPa, and the temperature of esterification is 250~260 DEG C, when the water quantity of distillate in esterification reaches theoretical Value 90% or more when be esterification terminal；

(2) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure 30~ Absolute pressure 500Pa being steadily evacuated to by normal pressure in 50min hereinafter, reaction temperature is 250~260 DEG C, the reaction time is 30~ 50min then proceedes to vacuumize, and carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure For 100Pa hereinafter, reaction temperature is 270~282 DEG C, the reaction time is 50~90min.

The preparation method of terylene advertising cloth as described above, the terephthalic acid (TPA), ethylene glycol, two with tert-butyl side group The molar ratio of first acid and 2,5,6,6- tetramethyl -2,5- heptandiols is 1:1.2~2.0:0.01~0.02:0.02~0.04, institute State catalyst, delustering agent and stabilizer additional amount be respectively 0.03~0.05wt% of terephthalic acid (TPA) additional amount, 0.20~ 0.25wt% and 0.01~0.05wt%.Binary acid with tert-butyl side group of the invention and 2,5,6,6- tetramethyl -2,5- heptan The additive amount of glycol preferably range both can guarantee that modified fiber had good mechanical property and crystallinity, while can also The peel strength for significantly improving terylene advertising cloth, is conducive to the production and application of fiber, the binary acid with tert-butyl side group and 2, The additive amount of 5,6,6- tetramethyl -2,5- heptandiols can appropriate adjustment according to actual needs, but should not too, adding too much pair The regularity destruction of polyester macromolecule structure is too big, excessive to the crystallinity and Effect on Mechanical Properties of fiber, is unfavorable for fiber Production and application, too low then peel strength is promoted unobvious.

The preparation method of terylene advertising cloth as described above, the catalyst are antimony oxide, antimony glycol or acetic acid Antimony, the delustering agent are titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.

The preparation method of terylene advertising cloth as described above, the inherent viscosity of modified poly ester is after the solid phase polycondensation viscosifies 1.0~1.2dL/g.

The preparation method of terylene advertising cloth as described above, the spinning technology parameter of the modified polyester industrial yarns are as follows:

It stretches, the technological parameter of thermal finalization are as follows:

The temperature of the calender lamination is 165~170 DEG C, and pressure is 5~5.5MPa, and the time is 75~90s.

Spinning technique of the invention is not limited to that, only enumerates a kind of feasible technical solution herein.Concrete technology ginseng Number is also not limited to this, can be adjusted according to actual needs.

The present invention also provides terylene advertising cloth made from a kind of preparation method using terylene advertising cloth as described above, tools There is lamination layer structure, is mainly made of modified polyester industrial yarns woven layer and PVC film layer；

The strand of the modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment, the binary with tert-butyl side group Sour segment and 2,5,6,6- tetramethyl -2,5- heptandiol segment.

As a preferred technical scheme:

Terylene advertising cloth as described above, the filament number of modified polyester industrial yarns are 2~3dtex, and multifilament fiber number is 300 ~500dtex, breaking strength >=7.0cN/dtex, line density deviation ratio are ± 1.5%, breaking strength CV value≤3.0%, fracture Elongation is 13.0~16.5%, and the central value of the elongation of extension at break CV value≤8.0%, 4.0cN/dtex load is 5.5 ~7.0%, dry-hot shrinkage under the conditions of 177 DEG C × 10min × 0.05cN/dtex is 5.8~9.2%, and internet pricing is (5 ~8) ± 2/m, oil content are 0.6 ± 0.2wt%, and the present invention is by introducing the binary acid with tert-butyl side group and 2,5,6,6- Tetramethyl -2,5- heptandiol is modified polyester, and the above-mentioned mechanical property of obtained industrial yarn does not decline, with existing skill Art is suitable；

PVC film is located at the bilateral of modified polyester industrial yarns woven cloths, unilateral PVC film with a thickness of 30~60 μm；

The grammes per square metre of terylene advertising cloth is 150~200g/m², warp tensile strength is >=110N/cm, and weft tensile strength is >=110N/cm, tearing strength >=35N/cm, peel strength >=10N/cm, use temperature range are -30 DEG C~+60 DEG C, the present invention Terylene advertising cloth peel strength and tearing strength be higher than the prior art, be primarily due to the present invention to the material of terylene advertising cloth Matter improves, and is introduced in polyester molecule chain with the binary acid segment of tert-butyl side group and 2,5,6,6- tetramethyls -2,5- Heptandiol segment, the binary acid with tert-butyl side group and 2, the presence meeting of the tert-butyl in 5,6,6- tetramethyl -2,5- heptandiols Cause the variation of main chain activity, to change the interaction force between chain element, the distance between molecule chain element can also be sent out Raw corresponding change, as a result leads to the increase of polymer cavity free volume, the increase of empty free volume increases the bonding of PVC Into the molecule reactive group such as-NH in agent₂,-OH ,-COOH etc. diffused into fiber gap during heat treatment, obtain Good interface combines, thus improves the adhesive effect between fiber and PVC film, so that peel strength, tearing strength obtain one Fixed raising.

Invention mechanism:

Macromolecular chain in polymer is not closely to pile up completely, always with the presence of gap between macromolecular chain, this Portion void volume is free volume.It penetrates into small molecule inside macromolecule, to have foot in macromolecule or between macromolecule Enough big gaps, so pore size (the i.e. ruler of free volume in the permeability and diffusivity of small molecule and macromolecular structure It is very little) it is related, in a certain range, the size of free volume is bigger, and the permeability of small molecule is higher, and diffusivity is better.Free body Product is divided into empty free volume and slit free volume again, and empty free body has bigger bulk compared with slit free volume, Promotion for the permeability of small molecule, empty free volume are more obvious compared with slit free volume effect.

The size and type of free volume depend primarily on the structure of polymer, and the principal element for influencing polymer architecture is Steric hindrance, side group size, side group structure etc..When position a certain on main polymer chain is replaced by side group, necessarily cause main chain The variation of activity, to change the interaction force of chain and interchain, chain can also occur to change accordingly at a distance from interchain, As a result lead to the variation of cohesive energy and free volume, polarity, size, length of the substituent group on polymer side chain etc. are to strand Rigid, intermolecular interaction so that the fractional free volume of polymer architecture all have a certain impact, therefore, substituent group The effect that difference generates is different, and the permeability and separation performance for often leading to polymer is also different.

For ethylene glycol dihydric alcohol straight chain molecule, the C atom on main chain is arranged in indention one on the other, works as main chain Two H atoms on some upper methylene are by methyl (- CH₃) when replacing, C atom and main chain C atom in the two side groups are not In the same plane, then, four sp3 hybridized orbits on the C of center are Chong Die with the unoccupied orbital on four C atoms around respectively, Four identical σ keys are formed, are arranged in positive tetrahedron, four carbon atom is located at four vertex of positive tetrahedron, when When three hydrogen of methyl are further replaced by methyl, it is at this moment equivalent to tert-butyl substitution, forms a bigger tetrahedron knot Structure, the strand that this strand in the arrangement of positive tetrahedron shape is arranged relative to indention, empty free volume obviously increase It is big very much, the permeability and diffusivity of small molecule can be significantly improved；And when two H atoms on main chain on some methylene When chain substituent of being drawn money on credit replaces, what is mainly increased is slit free volume, and it is smaller to increase amplitude, to the permeability of small molecule and Diffusible promotion effect is limited, simultaneously because the rigidity for chain substituent of drawing money on credit is smaller, entanglement is easy to happen between strand, no Conducive to the increase of free volume.

For the straight chain molecules such as M-phthalic acid and own dioctyl phthalate, when on M-phthalic acid phenyl ring H atom or oneself two H atom on formic acid methylene is by methyl (- CH₃) when replacing, C atom and main chain C atom in side group not in the same plane, Then, four sp3 hybridized orbits on the C of center are Chong Die with the unoccupied orbital on four C atoms around respectively, form four complete phases With σ key, arranged in positive tetrahedron, four carbon atom is located at four vertex of positive tetrahedron, when methyl three hydrogen into When one step is replaced by methyl, it is at this moment equivalent to tert-butyl substitution, forms a bigger tetrahedral structure, this positive tetrahedron The strand of arrangement is arranged with respect to indention, and empty free volume significantly increases very much, can significantly improve small molecule Permeability and diffusivity；And when the H atom on M-phthalic acid phenyl ring or the H atom on own dioctyl phthalate methylene are by long-chain branch When substituent group replaces, what is mainly increased is slit free volume, and it is smaller to increase amplitude, permeability to small molecule and diffusible Promotion effect is limited, simultaneously because the rigidity for chain substituent of drawing money on credit is smaller, entanglement is easy to happen between strand, is unfavorable for freedom The increase of volume.

The present invention in polyester molecule chain by introducing 2,5,6,6- tetramethyl -2,5- heptandiol and with tert-butyl side group Binary acid has been obviously improved the peel strength of terylene advertising cloth, and the structural formula of 2,5,6,6- tetramethyl -2,5- heptandiols is as follows:

Binary acid with tert-butyl side group is 5- tert-butyl -1,3- phthalic acid, the own dioctyl phthalate of 2- tert-butyl -1,6-, 3- The own dioctyl phthalate of tert-butyl -1,6- or 2, the own dioctyl phthalate of 5- di-t-butyl -1,6-, the wherein own dioctyl phthalate of 2- tert-butyl -1,6-, uncle 3- The own dioctyl phthalate of butyl -1,6- and 2, the own dioctyl phthalate of 5- di-t-butyl -1,6- are adipic acid, are a kind of fatty acid, rigidity is less than 5- tert-butyl -1,3- phthalic acid is conducive to the flexibility for promoting polyester segment；

The presence of tert-butyl can cause to lead in 2,5,6,6- tetramethyl -2,5- heptandiol and binary acid with tert-butyl side group The variation of chain activity, thus the interaction force between changing chain element, the distance between molecule chain element can also occur accordingly Change, cause the empty free volume of modified poly ester to increase.Compared with short-chain branch substituent group (such as methyl, ethyl group), Tert-butyl occupies biggish spatial position, and bigger free volume will be obtained in the mode of strand arrangement；With long-chain branch Substituent group is compared, and what one side tert-butyl increased is empty free volume, and draw money on credit chain substituent increase is slit free body The rigidity of product, another aspect tert-butyl is greater than chain substituent of drawing money on credit, and reduces the entanglement between strand, thus tert-butyl is longer Branched alkyl substituent has more free volumes in the mode that strand arranges.The increase of empty free volume makes gluing for PVC Close the molecule reactive group such as-NH in promoting agent₂,-OH ,-COOH etc. diffused into fiber gap during heat treatment, It obtains good interface to combine, thus improves the adhesive effect between fiber and PVC film, so that peel strength, tearing strength obtain Obtain raising centainly.

The utility model has the advantages that

(1) preparation method of a kind of terylene advertising cloth of the invention, simple process and low cost, by drawing in the polyester Enter 2,5,6,6- tetramethyl -2,5- heptandiol of band and the binary acid with tert-butyl side group is modified polyester, increases polyester Empty free volume, significantly improve the peel strength of terylene advertising cloth with adhesion promoter cooperation；

(2) a kind of terylene advertising cloth of the invention, peel strength is good, and good mechanical property has a extensive future.

Specific embodiment

The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.

Embodiment 1

The preparation method of terylene advertising cloth, steps are as follows:

(1) modified poly ester is prepared；

(1.1) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:

(a) by the molar ratio of 1:1:1.2:2.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl-2-butanone It is mixed with isopropyl ether, 2h is reacted under condition of ice bath, carry out crystallisation by cooling, centrifuge separation, washing, purification after reaction and done It is dry to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2:10:0.01, in 40 DEG C of temperature condition Lower reaction 50min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

(1.2) esterification；

By terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiol and 5- tert-butyl -1,3- phthalic acid It is made into slurry, antimony oxide, titanium dioxide and triphenyl phosphate is added after mixing, pressurization carries out ester in nitrogen atmosphere Change reaction, moulding pressure 0.1MPa, the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches theoretical Value 90% when be esterification terminal, wherein terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiols and 5- The molar ratio of tert-butyl -1,3- phthalic acid is 1:1.2:0.01:0.025, antimony oxide, titanium dioxide and triphenyl phosphate Additional amount be respectively terephthalic acid (TPA) additional amount 0.03wt%, 0.22wt% and 0.01wt%；

(1.3) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30min The interior absolute pressure that is steadily evacuated to by normal pressure is 500, and reaction temperature is 260 DEG C, and reaction time 30min then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 60Pa, and reaction temperature is 280 DEG C, Reaction time is 50min；

(2) modified polyester industrial yarns are prepared；

By by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type and winding, and the inherent viscosity of modified poly ester is 1.1dL/g, spinning technique after solid phase polycondensation thickening Parameter is as follows:

It stretches, the technological parameter of thermal finalization are as follows:

The filament number of modified polyester industrial yarns is 2dtex, and multifilament fiber number is 450dtex, breaking strength 7.3cN/ Dtex, line density deviation ratio are -0.5%, and breaking strength CV value is 2.8%, elongation at break 16.5%, extension at break CV value Central value for the elongation of 7.9%, 4.0cN/dtex load is 6.0%, in 177 DEG C × 10min × 0.05cN/dtex condition Under dry-hot shrinkage be 5.8%, internet pricing be 8/m, oil content 0.8wt%；

(3) terylene advertising cloth is prepared；

Modified polyester industrial yarns are carried out warping, weaving and calender lamination PVC film fabric construction is made being washing for 1/1 plain weave Synthetic fibre advertising cloth, wherein weaving is carried out using biaxial warp knitting machine, primary coat is also carried out before calender lamination, primary coat refers to By paste PVC (paste PVC, diethyl phthalate, zinc-tin stabilizer, toluene diisocyanate containing adhesive at 30 DEG C Mixture of the poly- isocyanurate weight ratio of acid for 100:50:1:0.3, the model P440 of paste PVC, the degree of polymerization are 1500) after being coated in terylene base fabric, the precuring 35s at 140 DEG C then carries out PVC pressure in precuring treated base fabric Prolong fitting, the temperature of calender lamination is 165 DEG C, pressure 5MPa, time 80s.

Final terylene advertising cloth obtained, has lamination layer structure, mainly by modified polyester industrial yarns woven layer and PVC Film layer composition, PVC film are located at the bilateral of modified polyester industrial yarns woven cloths, unilateral PVC film with a thickness of 60 μm；

The grammes per square metre of terylene advertising cloth is 180g/m², warp tensile strength 110N/cm, weft tensile strength 130N/ Cm, tearing strength 38N/cm, peel strength 11N/cm, use temperature range are -30~+60 DEG C.

Comparative example 1

A kind of preparation method of terylene advertising cloth, preparation step is substantially the same manner as Example 1, the difference is that, do not add Add 2,5,6,6- tetramethyl -2,5- heptandiols and 5- tert-butyl -1,3- phthalic acid, i.e., polyester is not modified, it is obtained The filament number of polyester industrial fiber is 2dtex, and multifilament fiber number is 450dtex, breaking strength 7.5cN/dtex, line density deviation Rate is -0.5%, and breaking strength CV value is 2.8%, elongation at break 15.5%, and extension at break CV value is 7.9%, 4.0cN/ The central value of the elongation of dtex load is 6.0%, dry-hot shrinkage under the conditions of 177 DEG C × 10min × 0.05cN/dtex It is 5.5%, internet pricing is 8/m, oil content 0.8wt%；The grammes per square metre of final terylene advertising cloth obtained is 180g/m², warp It is 110N/cm, weft tensile strength 132N/cm, tearing strength 7N/cm to tensile strength, peel strength 7N/cm makes It is -20 DEG C~+50 DEG C with temperature range.

Embodiment 1 and comparative example 1 are compared it is found that the difference of this example and terylene advertising cloth of the invention is that its material is Conventional polyester.Terylene advertising cloth produced by the present invention significantly increases compared to the breaking strength and tensile strength of conventional polyester advertising cloth Add.

Comparative example 2

A kind of preparation method of terylene advertising cloth, preparation step is substantially the same manner as Example 1, the difference is that, step (1) 2,5,6,6- tetramethyl -2,5- heptandiols and 5- tert-butyl -1,3- phthalic acid are substituted using 1,2 dodecanediols in, The filament number of polyester industrial fiber obtained is 2dtex, and multifilament fiber number is 450dtex, breaking strength 7.3cN/dtex, and line is close Spending deviation ratio is -0.5%, and breaking strength CV value is 2.8%, elongation at break 15.8%, and extension at break CV value is 7.9%, The central value of the elongation of 4.0cN/dtex load is 6.0%, xeothermic under the conditions of 177 DEG C × 10min × 0.05cN/dtex Shrinking percentage is 5.5%, and internet pricing is 8/m, oil content 0.8wt%；The grammes per square metre of final terylene advertising cloth obtained is 180g/ m², warp tensile strength 110N/cm, weft tensile strength 132N/cm, tearing strength 6.8N/cm, peel strength is 6.7N/cm, use temperature range are -20 DEG C~+50 DEG C.

It compares with embodiment 1 it can be found that 2,5,6,6- tetramethyl -2,5- heptandiols and 5- tert-butyl -1,3- benzene diformazan Acid is more advantageous to the breaking strength and stretching for promoting terylene advertising cloth relative to 1,2 dodecanediols containing chain substituent of drawing money on credit The mechanical properties such as intensity, this is primarily due on the one hand 2,5,6,6- tetramethyl -2,5- heptandiols and 5- tert-butyl -1,3- benzene two The free volume that tert-butyl in formic acid increases is more empty free volume, and the long-chain branch in 1,2 dodecanediol Substituent group increase free volume be more slit free volume, on the other hand 2,5,6,6- tetramethyl -2,5- heptandiols and The rigidity of tert-butyl in 5- tert-butyl -1,3- phthalic acid is all larger than the chain substituent of drawing money on credit in 1,2 dodecanediols, subtracts Lacked the entanglement between strand, thus 2,5,6,6- tetramethyl -2,5- heptandiols and 5- tert-butyl -1,3- phthalic acid compared with 1, 2 dodecanediols have more free volumes in the mode that polyester molecule chain arranges, and make in diethyl phthalate Molecule reactive group such as-NH₂,-OH ,-COOH etc. diffused into fiber gap during heat treatment, obtain good boundary Face combines, thus improves the adhesive effect between fiber and PVC film, so that peel strength, tearing strength obtain certain mention It is high.

Embodiment 2

The preparation method of terylene advertising cloth, steps are as follows:

(1) modified poly ester is prepared；

(1.1) it prepares the own dioctyl phthalate of 2- tert-butyl -1,6-: wolframic acid and hydrogen peroxide being mixed first, are stirred at room temperature Then 10min is added 2- tert. butyl cyclohexanol and first reacts 1h under the conditions of 80 DEG C of temperature, then is warming up to 94 DEG C of reaction 2h, instead During answering, reactant is in reflux state always, finally carries out crystallisation by cooling, washing and purification, wherein when reaction starts, tungsten Sour, the pure and mild hydrogen peroxide of 2- t-butylcyclohexyl molar ratio is 1:35:120；

(1.2) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:

(a) by the molar ratio of 1.1:1:1.2:2.3 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- fourth Ketone and isopropyl ether mixing, 2h is reacted under condition of ice bath, after reaction carry out crystallisation by cooling, centrifuge separation, washing, purification and It is dried to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2:10:0.01, in 45 DEG C of temperature condition Lower reaction 50min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiol and the own dioctyl phthalate of 2- tert-butyl -1,6- It is made into slurry, antimony oxide, titanium dioxide and trimethyl phosphate is added after mixing, pressurization carries out ester in nitrogen atmosphere Change reaction, moulding pressure is normal pressure, and the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical value 96% when be esterification terminal, wherein terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiols and uncle 2- The molar ratio of the own dioctyl phthalate of butyl -1,6- is 1:1.2:0.02:0.02, antimony oxide, titanium dioxide and trimethyl phosphate Additional amount is respectively 0.04wt%, 0.20wt% and 0.04wt% of terephthalic acid (TPA) additional amount；

(1.4) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 35min The interior absolute pressure that is steadily evacuated to by normal pressure is 450Pa, and reaction temperature is 255 DEG C, reaction time 40min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 100Pa, reaction temperature 270 DEG C, reaction time 60min；

(2) modified polyester industrial yarns are prepared；

By by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type and winding, and the inherent viscosity of modified poly ester is 1.1dL/g, spinning technique after solid phase polycondensation thickening Parameter is as follows:

It stretches, the technological parameter of thermal finalization are as follows:

The filament number of modified polyester industrial yarns is 3dtex, and multifilament fiber number is 300dtex, breaking strength 7.2cN/ Dtex, line density deviation ratio are 0%, and breaking strength CV value is 3.0%, elongation at break 14.5%, and extension at break CV value is The central value of the elongation of 7.85%, 4.0cN/dtex load is 6.0%, in 177 DEG C × 10min × 0.05cN/dtex condition Under dry-hot shrinkage be 9.2%, internet pricing be 3/m, oil content 0.6wt%；

(3) terylene advertising cloth is prepared；

Modified polyester industrial yarns are carried out warping, weaving and calender lamination PVC film fabric construction is made being washing for 1/1 plain weave Synthetic fibre advertising cloth, wherein weaving is carried out using biaxial warp knitting machine, primary coat is also carried out before calender lamination, primary coat refers to By paste PVC (paste PVC, diethyl phthalate, zinc-tin stabilizer, toluene diisocyanate containing adhesive at 50 DEG C Mixture of the poly- isocyanurate weight ratio of acid for 100:60:2:2.0, the model P440 of paste PVC, the degree of polymerization are 1500) after being coated in terylene base fabric, the precuring 45s at 160 DEG C then carries out PVC pressure in precuring treated base fabric Prolong fitting, the temperature of calender lamination is 165 DEG C, pressure 5.5MPa, time 75s.

Final terylene advertising cloth obtained, has lamination layer structure, mainly by modified polyester industrial yarns woven layer and PVC Film layer composition, PVC film are located at the bilateral of modified polyester industrial yarns woven cloths, unilateral PVC film with a thickness of 45 μm；

The grammes per square metre of terylene advertising cloth is 170g/m², warp tensile strength 110N/cm, weft tensile strength 120N/ Cm, tearing strength 38N/cm, peel strength 14N/cm, use temperature range are -25~+60 DEG C.

Embodiment 3

The preparation method of terylene advertising cloth, steps are as follows:

(1) modified poly ester is prepared；

(1.1) it prepares the own dioctyl phthalate of 2- tert-butyl -1,6-: wolframic acid and hydrogen peroxide being mixed first, are stirred at room temperature Then 12min is added 2- tert. butyl cyclohexanol and first reacts 1.5h under the conditions of 83 DEG C of temperature, then is warming up to 90 DEG C of reaction 2h, In reaction process, reactant is in reflux state always, finally carries out crystallisation by cooling, washing and purification, wherein when reaction starts, Wolframic acid, the pure and mild hydrogen peroxide of 2- t-butylcyclohexyl molar ratio be 1:33:120；

(1.2) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:

(a) by the molar ratio of 1.2:1:1.25:2.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- Butanone and isopropyl ether mixing, 3h is reacted under condition of ice bath, carries out crystallisation by cooling, centrifuge separation, washing, purification after reaction Be dried to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 3:10:0.03, in 40 DEG C of temperature condition Lower reaction 50min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiol and the own dioctyl phthalate of 2- tert-butyl -1,6- It is made into slurry, antimony glycol, titanium dioxide and Trimethyl phosphite is added after mixing, pressurization carries out ester in nitrogen atmosphere Change reaction, moulding pressure 0.3MPa, the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification reaches theoretical Value 93% when be esterification terminal, wherein terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiols and 2- The molar ratio of the own dioctyl phthalate of tert-butyl -1,6- is 1:1.5:0.01:0.02, antimony glycol, titanium dioxide and Trimethyl phosphite Additional amount be respectively terephthalic acid (TPA) additional amount 0.05wt%, 0.24wt% and 0.03wt%；

(1.4) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 40min The interior absolute pressure that is steadily evacuated to by normal pressure is 460Pa, and reaction temperature is 256 DEG C, reaction time 50min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 90Pa, reaction temperature 280 DEG C, reaction time 70min；

(2) modified polyester industrial yarns are prepared；

By by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type and winding, and the inherent viscosity of modified poly ester is 1.0dL/g, spinning technique after solid phase polycondensation thickening Parameter is as follows:

It stretches, the technological parameter of thermal finalization are as follows:

The filament number of modified polyester industrial yarns is 2dtex, and multifilament fiber number is 300dtex, breaking strength 7.1cN/ Dtex, line density deviation ratio are -1.5%, and breaking strength CV value is 2.92%, elongation at break 13.0%, extension at break CV Value is that the central value of the elongation of 8.0%, 4.0cN/dtex load is 7.0%, in 177 DEG C × 10min × 0.05cN/dtex item Dry-hot shrinkage under part is 8.8%, and internet pricing is 5/m, oil content 0.4wt%；

(3) terylene advertising cloth is prepared；

Modified polyester industrial yarns are carried out warping, weaving and calender lamination PVC film fabric construction is made being washing for 1/1 plain weave Synthetic fibre advertising cloth, wherein weaving is carried out using biaxial warp knitting machine, primary coat is also carried out before calender lamination, primary coat refers to By paste PVC (paste PVC, diethyl phthalate, zinc-tin stabilizer, toluene diisocyanate containing adhesive at 40 DEG C Mixture of the poly- isocyanurate weight ratio of acid for 100:55:1.5:1.2, the model P440 of paste PVC, the degree of polymerization are 1500) after being coated in terylene base fabric, the precuring 40s at 150 DEG C then carries out PVC pressure in precuring treated base fabric Prolong fitting, the temperature of calender lamination is 167 DEG C, pressure 5MPa, time 75s.

Final terylene advertising cloth obtained, has lamination layer structure, mainly by modified polyester industrial yarns woven layer and PVC Film layer composition, PVC film are located at the bilateral of modified polyester industrial yarns woven cloths, unilateral PVC film with a thickness of 30 μm；

The grammes per square metre of terylene advertising cloth is 200g/m², warp tensile strength 110N/cm, weft tensile strength 110N/ Cm, tearing strength 40N/cm, peel strength 20N/cm, use temperature range are -30~+55 DEG C.

Embodiment 4

The preparation method of terylene advertising cloth, steps are as follows:

(1) modified poly ester is prepared；

(1.1) it prepares the own dioctyl phthalate of 3- tert-butyl -1,6-: wolframic acid and hydrogen peroxide being mixed first, are stirred at room temperature Then 13min is added 4- tert. butyl cyclohexanol and first reacts 2h under the conditions of 85 DEG C of temperature, then is warming up to 90 DEG C of reaction 3h, instead During answering, reactant is in reflux state always, finally carries out crystallisation by cooling, washing and purification, wherein when reaction starts, tungsten Sour, the pure and mild hydrogen peroxide of 4- t-butylcyclohexyl molar ratio is 1:30:130；

(1.2) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:

(a) by the molar ratio of 1.2:1:1.3:2.5 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- fourth Ketone and isopropyl ether mixing, 3h is reacted under condition of ice bath, after reaction carry out crystallisation by cooling, centrifuge separation, washing, purification and It is dried to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2.5:10:0.02, in 45 DEG C of temperature strip 60min is reacted under part, hydrogen is continually fed into reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiol and the own dioctyl phthalate of 3- tert-butyl -1,6- It is made into slurry, antimony glycol, titanium dioxide and triphenyl phosphate is added after mixing, pressurizes and is esterified in nitrogen atmosphere Reaction, moulding pressure 0.2MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical value 91% when be esterification terminal, wherein terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiols and uncle 3- The molar ratio of the own dioctyl phthalate of butyl -1,6- is 1:1.7:0.015:0.04, antimony glycol, titanium dioxide and triphenyl phosphate plus Enter 0.05wt%, 0.25wt% and 0.05wt% that amount is respectively terephthalic acid (TPA) additional amount；

(1.4) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 45min The interior absolute pressure that is steadily evacuated to by normal pressure is 470Pa, and reaction temperature is 250 DEG C, reaction time 50min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 80Pa, reaction temperature 275 DEG C, reaction time 80min；

(2) modified polyester industrial yarns are prepared；

By by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type and winding, and the inherent viscosity of modified poly ester is 1.2dL/g, spinning technique after solid phase polycondensation thickening Parameter is as follows:

It stretches, the technological parameter of thermal finalization are as follows:

The filament number of modified polyester industrial yarns is 2.2dtex, and multifilament fiber number is 500dtex, breaking strength 7.0cN/ Dtex, line density deviation ratio are 1.0%, and breaking strength CV value is 2.7%, elongation at break 13.0%, extension at break CV value Central value for the elongation of 8.0%, 4.0cN/dtex load is 5.5%, in 177 DEG C × 10min × 0.05cN/dtex condition Under dry-hot shrinkage be 6.9%, internet pricing be 8/m, oil content 0.6wt%；

(3) terylene advertising cloth is prepared；

Modified polyester industrial yarns are carried out warping, weaving and calender lamination PVC film fabric construction is made being washing for 1/1 plain weave Synthetic fibre advertising cloth, wherein the technological parameter of weaving and primary coat is with embodiment 1, and the temperature of calender lamination is 168 DEG C, and pressure is 5.2MPa, time 90s.

Final terylene advertising cloth obtained, has lamination layer structure, mainly by modified polyester industrial yarns woven layer and PVC Film layer composition, PVC film are located at the bilateral of modified polyester industrial yarns woven cloths, unilateral PVC film with a thickness of 30 μm；

The grammes per square metre of terylene advertising cloth is 150g/m², warp tensile strength 130N/cm, weft tensile strength 140N/ Cm, tearing strength 40N/cm, peel strength 10N/cm, use temperature range are -30 DEG C~+50 DEG C.

Embodiment 5

The preparation method of terylene advertising cloth, steps are as follows:

(1) modified poly ester is prepared；

(1.1) it prepares the own dioctyl phthalate of 3- tert-butyl -1,6-: wolframic acid and hydrogen peroxide being mixed first, are stirred at room temperature Then 14min is added 4- tert. butyl cyclohexanol and first reacts 2h under the conditions of 82 DEG C of temperature, then is warming up to 92 DEG C of reaction 3h, instead During answering, reactant is in reflux state always, finally carries out crystallisation by cooling, washing and purification, wherein when reaction starts, tungsten Sour, the pure and mild hydrogen peroxide of 4- t-butylcyclohexyl molar ratio is 1:40:130；

(1.2) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:

(a) by the molar ratio of 1:1:1.3:3.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl-2-butanone It is mixed with isopropyl ether, 4h is reacted under condition of ice bath, carry out crystallisation by cooling, centrifuge separation, washing, purification after reaction and done It is dry to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2.5:10:0.02, in 50 DEG C of temperature strip 55min is reacted under part, hydrogen is continually fed into reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiol and the own dioctyl phthalate of 3- tert-butyl -1,6- It is made into slurry, antimony acetate, titanium dioxide and trimethyl phosphate is added after mixing, pressurization be esterified anti-in nitrogen atmosphere It answers, moulding pressure is normal pressure, and the temperature of esterification is 258 DEG C, when the water quantity of distillate in esterification reaches theoretical value It is esterification terminal, wherein terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiols and 3- tertiary fourth when 95% The molar ratio of the own dioctyl phthalate of base -1,6- is 1:2.0:0.016:0.03, the additional amount of antimony acetate, titanium dioxide and trimethyl phosphate Respectively 0.04wt%, 0.23wt% and 0.04wt% of terephthalic acid (TPA) additional amount；

(1.4) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 50min The interior absolute pressure that is steadily evacuated to by normal pressure is 410Pa, and reaction temperature is 257 DEG C, reaction time 38min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 85Pa, reaction temperature 282 DEG C, reaction time 90min；

(2) modified polyester industrial yarns are prepared；

By by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type and winding, and the inherent viscosity of modified poly ester is 1.0dL/g, spinning technique after solid phase polycondensation thickening Parameter is as follows:

It stretches, the technological parameter of thermal finalization are as follows:

The filament number of modified polyester industrial yarns is 2.6dtex, and multifilament fiber number is 400dtex, breaking strength 7.3cN/ Dtex, line density deviation ratio are 0.5%, and breaking strength CV value is 2.88%, elongation at break 16.5%, extension at break CV value Central value for the elongation of 7.8%, 4.0cN/dtex load is 5.5%, in 177 DEG C × 10min × 0.05cN/dtex condition Under dry-hot shrinkage be 5.8%, internet pricing be 8/m, oil content 0.8wt%；

(3) terylene advertising cloth is prepared；

Modified polyester industrial yarns are carried out warping, weaving and calender lamination PVC film fabric construction is made being washing for 1/1 plain weave Synthetic fibre advertising cloth, wherein the technological parameter of weaving and primary coat is with embodiment 2, and the temperature of calender lamination is 170 DEG C, and pressure is 5.1MPa, time 85s.

Final terylene advertising cloth obtained, has lamination layer structure, mainly by modified polyester industrial yarns woven layer and PVC Film layer composition, PVC film are located at the bilateral of modified polyester industrial yarns woven cloths, unilateral PVC film with a thickness of 60 μm；

The grammes per square metre of terylene advertising cloth is 150g/m², warp tensile strength 115N/cm, weft tensile strength 120N/ Cm, tearing strength 35N/cm, peel strength 14N/cm, use temperature range are -25 DEG C~+60 DEG C.

Embodiment 6

The preparation method of terylene advertising cloth, steps are as follows:

(1) modified poly ester is prepared；

(1.1) it prepares the own dioctyl phthalate of 2,5- di-t-butyl -1,6-: first mixing wolframic acid and hydrogen peroxide, at room temperature 15min is stirred, 2,4- di-t-butyl cyclohexanol is then added and first reacts 1.5h under the conditions of 83 DEG C of temperature, then is warming up to 92 DEG C 2.5h is reacted, in reaction process, reactant is in reflux state always, crystallisation by cooling, washing and purification is finally carried out, wherein instead When should start, the molar ratio of wolframic acid, 2,4- di-t-butyl cyclohexanol and hydrogen peroxide is 1:40:120；

(1.2) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:

(a) by the molar ratio of 1.1:1:1.2:3.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- fourth Ketone and isopropyl ether mixing, 4h is reacted under condition of ice bath, after reaction carry out crystallisation by cooling, centrifuge separation, washing, purification and It is dried to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 3:10:0.03, in 50 DEG C of temperature condition Lower reaction 60min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiol and 2,5- di-t-butyl -1,6- oneself two Formic acid is made into slurry, and antimony acetate, titanium dioxide and Trimethyl phosphite is added after mixing, pressurizes and carries out in nitrogen atmosphere Esterification, moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches reason By value 90% when be esterification terminal, wherein terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiols and The molar ratio of the own dioctyl phthalate of 2,5- di-t-butyls -1,6- is 1:2.0:0.02:0.04, antimony acetate, titanium dioxide and phosphorous acid three The additional amount of methyl esters is respectively 0.03wt%, 0.25wt% and 0.01wt% of terephthalic acid (TPA) additional amount；

(1.4) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 35min The interior absolute pressure that is steadily evacuated to by normal pressure is 400Pa, and reaction temperature is 253 DEG C, reaction time 30min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 100Pa, reaction temperature 274 DEG C, reaction time 65min；

(2) modified polyester industrial yarns are prepared；

By by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type and winding, and the inherent viscosity of modified poly ester is 1.0dL/g, spinning technique after solid phase polycondensation thickening Parameter is as follows:

It stretches, the technological parameter of thermal finalization are as follows:

The filament number of modified polyester industrial yarns is 3dtex, and multifilament fiber number is 500dtex, breaking strength 7.0cN/ Dtex, line density deviation ratio are 1.5%, and breaking strength CV value is 2.83%, elongation at break 15.5%, extension at break CV value Central value for the elongation of 7.9%, 4.0cN/dtex load is 5.5%, in 177 DEG C × 10min × 0.05cN/dtex condition Under dry-hot shrinkage be 5.8%, internet pricing be 10/m, oil content 0.4wt%；

(3) terylene advertising cloth is prepared；

Modified polyester industrial yarns are carried out warping, weaving and calender lamination PVC film fabric construction is made being washing for 1/1 plain weave Synthetic fibre advertising cloth, wherein the technological parameter of weaving and primary coat is with embodiment 3, and the temperature of calender lamination is 170 DEG C, and pressure is 5.5MPa, time 90s.

Final terylene advertising cloth obtained, has lamination layer structure, mainly by modified polyester industrial yarns woven layer and PVC Film layer composition, PVC film are located at the bilateral of modified polyester industrial yarns woven cloths, unilateral PVC film with a thickness of 50 μm；

The grammes per square metre of terylene advertising cloth is 150g/m², warp tensile strength 135N/cm, weft tensile strength 115N/ Cm, tearing strength 38N/cm, peel strength 17N/cm, use temperature range are -30 DEG C~+40 DEG C.

Embodiment 7

The preparation method of terylene advertising cloth, steps are as follows:

(1) modified poly ester is prepared；

(1.1) it prepares the own dioctyl phthalate of 2,5- di-t-butyl -1,6-: first mixing wolframic acid and hydrogen peroxide, at room temperature 11min is stirred, 2,4- di-t-butyl cyclohexanol is then added and first reacts 1h under the conditions of 80 DEG C of temperature, then is warming up to 95 DEG C instead Answer 2.2h, in reaction process, reactant is in reflux state always, crystallisation by cooling, washing and purification is finally carried out, wherein reacting When beginning, the molar ratio of wolframic acid, 2,4- di-t-butyl cyclohexanol and hydrogen peroxide is 1:35:150；

(1.2) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:

(a) by the molar ratio of 1.2:1:1.2:3.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- fourth Ketone and isopropyl ether mixing, 3h is reacted under condition of ice bath, after reaction carry out crystallisation by cooling, centrifuge separation, washing, purification and It is dried to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 3:10:0.02, in 42 DEG C of temperature condition Lower reaction 55min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiol and 2,5- di-t-butyl -1,6- oneself two Formic acid is made into slurry, and antimony oxide, titanium dioxide and trimethyl phosphate is added after mixing, pressurize in nitrogen atmosphere into Row esterification, moulding pressure are normal pressure, and the temperature of esterification is 258 DEG C, when the water quantity of distillate in esterification reaches reason By value 95% when be esterification terminal, wherein terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiols and The molar ratio of the own dioctyl phthalate of 2,5- di-t-butyls -1,6- is 1:1.9:0.01:0.03, antimony oxide, titanium dioxide and phosphoric acid The additional amount of trimethyl is respectively 0.04wt%, 0.20wt% and 0.04wt% of terephthalic acid (TPA) additional amount；

(1.4) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 50min The interior absolute pressure that is steadily evacuated to by normal pressure is 410Pa, and reaction temperature is 257 DEG C, reaction time 38min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 85Pa, reaction temperature 277 DEG C, reaction time 90min；

(2) modified polyester industrial yarns are prepared；

By by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type and winding, and the inherent viscosity of modified poly ester is 1.1dL/g, spinning technique after solid phase polycondensation thickening Parameter is as follows:

It stretches, the technological parameter of thermal finalization are as follows:

The filament number of modified polyester industrial yarns is 2dtex, and multifilament fiber number is 370dtex, breaking strength 7.4cN/ Dtex, line density deviation ratio are -1.0%, and breaking strength CV value is 3.0%, elongation at break 16.5%, extension at break CV value Central value for the elongation of 8.0%, 4.0cN/dtex load is 7.0%, in 177 DEG C × 10min × 0.05cN/dtex condition Under dry-hot shrinkage be 9.2%, internet pricing be 6/m, oil content 0.4wt%；

(3) terylene advertising cloth is prepared；

Modified polyester industrial yarns are carried out warping, weaving and calender lamination PVC film fabric construction is made being washing for 1/1 plain weave Synthetic fibre advertising cloth, wherein the technological parameter of weaving and primary coat is 166 DEG C, pressure 5MPa with embodiment 1, the temperature of calender lamination, Time is 80s.

Final terylene advertising cloth obtained, has lamination layer structure, mainly by modified polyester industrial yarns woven layer and PVC Film layer composition, PVC film are located at the bilateral of modified polyester industrial yarns woven cloths, unilateral PVC film with a thickness of 60 μm；

The grammes per square metre of terylene advertising cloth is 200g/m², warp tensile strength 110N/cm, weft tensile strength 125N/ Cm, tearing strength 39N/cm, peel strength 10N/cm, use temperature range are -20 DEG C~+55 DEG C.

Claims (10)

1. the preparation method of terylene advertising cloth, it is characterized in that: modified polyester industrial yarns are carried out warping, weaving and calender lamination Terylene advertising cloth is made in PVC film；

The modified polyester industrial yarns are by the way that modified poly ester melt is carried out solid phase polycondensation thickening, melting, metering, extrusion, cold But, oil, stretch, made from thermal finalization and winding；

Before the solid phase polycondensation viscosifies modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, with tert-butyl side group Binary acid and 2,5,6,6- tetramethyl -2,5- heptandiol successively carry out esterification and polycondensation reaction after mixing；

Binary acid with tert-butyl side group is 5- tert-butyl -1,3- phthalic acid, the own dioctyl phthalate of 2- tert-butyl -1,6-, the tertiary fourth of 3- The own dioctyl phthalate of base -1,6- or 2, the own dioctyl phthalate of 5- di-t-butyl -1,6-, the structural formula of 2,5,6,6- tetramethyl -2,5- heptandiols It is as follows:

2. the preparation method of terylene advertising cloth according to claim 1, which is characterized in that described 2,5,6,6- tetramethyls- The synthesis step of 2,5- heptandiol is as follows:

(1) 1~1.2:1:1.2~1.3:2.0~3.0 molar ratio is pressed by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- bis- Methyl -2- butanone and isopropyl ether mixing, react 2~4h under condition of ice bath, carry out crystallisation by cooling, centrifugation point after reaction From, wash, refine and be dried to obtain octyne glycol；

(2) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2~3:10:0.01~0.03, at 40~50 DEG C 50~60min is reacted under the conditions of temperature, is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2, 5,6,6- tetramethyl -2,5- heptandiol.

3. the preparation method of terylene advertising cloth according to claim 2, which is characterized in that the 2- tert-butyl -1,6- oneself The synthetic method of dioctyl phthalate, the own dioctyl phthalate of 3- tert-butyl -1,6- and the own dioctyl phthalate of 2,5- di-t-butyl -1,6- are as follows:

Wolframic acid and hydrogen peroxide are mixed first, 10~15min is stirred at room temperature, raw alcohol is then added first at 80~85 DEG C Temperature under the conditions of react 1~2h, then be warming up to 90~95 DEG C of 2~3h of reaction, in reaction process, reactant is in reflux always State finally carries out crystallisation by cooling, washing and purification；

When reaction starts, the molar ratio of wolframic acid, raw alcohol and hydrogen peroxide is 1:30~40:120~150；

The own dioctyl phthalate of the 2- tert-butyl -1,6-, the own dioctyl phthalate of 3- tert-butyl -1,6- and the own diformazan of 2,5- di-t-butyl -1,6- The corresponding raw alcohol of acid is respectively 2- tert. butyl cyclohexanol, the pure and mild 2,4- di-t-butyl cyclohexanol of 4- t-butylcyclohexyl.

4. the preparation method of terylene advertising cloth according to claim 3, which is characterized in that change before the solid phase polycondensation thickening The preparation step of property polyester is as follows:

(1) esterification；

Terephthalic acid (TPA), ethylene glycol, the binary acid with tert-butyl side group and 2,5,6,6- tetramethyl -2,5- heptandiol are matched and are slurried Catalyst, delustering agent and stabilizer is added after mixing in material, and pressurization carries out esterification, moulding pressure in nitrogen atmosphere For normal pressure~0.3MPa, the temperature of esterification is 250~260 DEG C, when the water quantity of distillate in esterification reaches theoretical value It is esterification terminal when 90% or more；

(2) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30~50min Interior to be steadily evacuated to absolute pressure 500Pa hereinafter, reaction temperature is 250~260 DEG C by normal pressure, the reaction time is 30~50min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, so that reaction pressure is further reduced to absolute pressure 100Pa hereinafter, Reaction temperature is 270~282 DEG C, and the reaction time is 50~90min.

5. the preparation method of terylene advertising cloth according to claim 4, which is characterized in that the terephthalic acid (TPA), second two The molar ratio of alcohol, the binary acid with tert-butyl side group and 2,5,6,6- tetramethyl -2,5- heptandiol be 1:1.2~2.0:0.01~ 0.02:0.02~0.04, the additional amount of the catalyst, delustering agent and stabilizer are respectively the 0.03 of terephthalic acid (TPA) additional amount ~0.05wt%, 0.20~0.25wt% and 0.01~0.05wt%.

6. the preparation method of terylene advertising cloth according to claim 5, which is characterized in that the catalyst is three oxidations two Antimony, antimony glycol or antimony acetate, the delustering agent be titanium dioxide, the stabilizer be triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.

7. the preparation method of terylene advertising cloth according to claim 1, which is characterized in that change after the solid phase polycondensation thickening Property polyester inherent viscosity be 1.0~1.2dL/g.

8. the preparation method of terylene advertising cloth according to claim 1, which is characterized in that the modified polyester industrial yarns Spinning technology parameter is as follows:

It stretches, the technological parameter of thermal finalization are as follows:

The temperature of the calender lamination is 165~170 DEG C, and pressure is 5~5.5MPa, and the time is 75~90s.

9. terylene advertising cloth made from the preparation method using terylene advertising cloth as described in any one of claims 1 to 8, special Sign is: having lamination layer structure, is mainly made of modified polyester industrial yarns woven layer and PVC film layer；

The strand of the modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment, the diacid chains with tert-butyl side group Section and 2,5,6,6- tetramethyl -2,5- heptandiol segment.

10. terylene advertising cloth according to claim 9, which is characterized in that the filament number of modified polyester industrial yarns be 2~ 3dtex, multifilament fiber number are 300~500dtex, and breaking strength >=7.0cN/dtex, line density deviation ratio is ± 1.5%, fracture Intensity CV value≤3.0%, elongation at break are 13.0~16.5%, extension at break CV value≤8.0%, 4.0cN/dtex load The central value of elongation is 5.5~7.0%, and dry-hot shrinkage under the conditions of 177 DEG C × 10min × 0.05cN/dtex is 5.8 ~9.2%, internet pricing is (5~8) ± 2/m, and oil content is 0.6 ± 0.2wt%；

PVC film is located at the bilateral of modified polyester industrial yarns woven cloths, unilateral PVC film with a thickness of 30~60 μm；

The grammes per square metre of terylene advertising cloth is 150~200g/m², warp tensile strength be >=110N/cm, weft tensile strength be >= 110N/cm, tearing strength >=35N/cm, peel strength >=10N/cm, use temperature range are -30 DEG C~+60 DEG C.