CN102518003A - Preparation method for halogen-free flame retardant polyester labeled paper - Google Patents
Preparation method for halogen-free flame retardant polyester labeled paper Download PDFInfo
- Publication number
- CN102518003A CN102518003A CN2011104443490A CN201110444349A CN102518003A CN 102518003 A CN102518003 A CN 102518003A CN 2011104443490 A CN2011104443490 A CN 2011104443490A CN 201110444349 A CN201110444349 A CN 201110444349A CN 102518003 A CN102518003 A CN 102518003A
- Authority
- CN
- China
- Prior art keywords
- mass
- halogen
- parts
- phosphor
- containing flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a preparation method for halogen-free flame retardant polyester labeled paper. The method is characterized in that the method comprises the following steps: adopting butyl acrylate, ethylhexyl acrylate, acrylic acid, hydroxyethyl acrylate, ethyl methacrylate, a phosphorus-containing flame retardant monomer, a solvent, an initiator, and the like as raw materials to prepare a phosphorus-containing flame retardant acrylic acid pre-polymerization resin; preparing a phosphorus-containing flame retardant acrylic acid pressure sensitive adhesive; uniformly coating the phosphorus-containing flame retardant acrylic acid pressure sensitive adhesive on a halogen-free flame retardant polyester thin film; compounding the polyacrylate pressure sensitive adhesive-coated halogen-free flame retardant polyester thin film and a polyester release film; and carrying out ripening to prepare the halogen-free flame retardant polyester label product. With the present invention, the flame retardant and pressure sensitive adhesion property, the appearance and the environmental protection quality of the whole label product can be effectively improved, and the halogen-free flame retardant polyester labeled paper can meet the performance requirement of VTM-0 grade flame retardation.
Description
Technical field
The invention belongs to laminar product---the preparation method of label paper relates to a kind of preparation method of halogen-free antiflaming polyester label paper.The label paper product that adopts the present invention to prepare is applicable to the Product labelling in particular requirement places such as fire-retardant fireproof, resistant to elevated temperatures electrical equipment and electrical, household electrical appliances, battery, communications and transportation.
Background technology
At present, industries such as electronic apparatus, household electrical appliances, battery and communications and transportation adopt plastic sheeting mostly with label paper printing process as base material coating adhesive material.Wherein, polyester film is with its excellent water-fast, oily, chemical moral character, and insulating properties and certain heat-resisting quantity are widely used as the electronic apparatus label substrate.Acrylate pressure sensitive adhesive has characteristic and the price advantage that low temperature resistant preferably, high temperature resistant, durable, no pernicious gas is overflowed, usually as the first-selected adhesive material of making label.Along with the development of society and the progress of science and technology, safe and harmlessization requirements such as the non-halogen and fire protection flame retarding of environment improve day by day, the production and the use of label have also been had the requirement of halogen-free flameproof.
One Chinese patent application numbers 200980101125.0, publication number CN102131640A provide a kind of " fire-retardant multilayer labels "; It comprises the ground floor that contains polymer substrate and fire retardant---top coat; The second layer---basement membrane and the 3rd layer---contains the acryloid cement layer of fire retardant; Three layers of acting in conjunction make VTM-0 level (the burning grade of a kind of thin material in the U.S. UL laboratory standard) halogen-free flameproof label; Wherein the fire retardant in top coat and the adhesive phase has all adopted ammonium polyphosphate, and flame retardant effect is better, but ammonium polyphosphate belongs to outer addition type inoganic solids fire retardant; At first the compatibility of solid flame retardant and liquid adhesive or top layer coating is bad; Influence the outward appearance of product, outer in addition additive flame retardant with reduced the tack of pressure sensitive adhesive and held viscosity after acrylate pressure sensitive adhesive mixes, be difficult under the prerequisite that guarantees its anti-flammability guarantee that its pressure-sensitive reaches requirement.Simultaneously, basement membrane does not adopt fire proofing, only depends on the top coat and the adhesive phase that add fire retardant to be difficult to make the whole flame retardant rating of label to reach the VTM-0 level.
Summary of the invention
The object of the invention is intended to overcome above-mentioned deficiency of the prior art, provides that a kind of technology is easy, the preparation method of the halogen-free antiflaming polyester label paper of function admirable.Thereby a kind of label product of function admirable such as fire resistance, pressure sensitive adhesive pressure-sensitive adhesive performance of integral body is provided.
Content of the present invention is: the preparation method of halogen-free antiflaming polyester label paper is characterized in that comprising the following steps:
A, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
Under the room temperature 20～70 parts by mass butyl acrylates, 15～55 parts by mass Isooctyl acrylate monomers, 3～7 parts by mass acrylic acid, 2～5 parts by mass hydroxy-ethyl acrylates, 5～20 parts by mass EMAs, 10～30 parts by mass phosphor-containing flame-proof monomers, 50～150 parts by mass solvents and 0.1～2.0 parts by mass initator are joined in the agitated reactor that has condensation reflux unit; Condenser temperature is controlled at below 15 ℃; Stir with revolution 100～300rpm, mix; Under nitrogen protection, be warming up to 75～80 ℃ gradually, carry out copolyreaction 4～6h, stop heating; It is even and make the mass percentage content of solids reach 30%～33% to add (in right amount) solvent again, is cooled to room temperature, makes phosphorous acrylic acid pre-polymerization resin, subsequent use;
Said phosphor-containing flame-proof monomer is the compound that contains two keys and bound phosphate groups;
Said solvent is a kind of in ethyl acetate, the toluene or two kinds;
Said initator is a kind of in benzoyl peroxide, the azo-bis-isobutyl cyanide or two kinds;
B, preparation phosphor-containing flame-proof acrylate pressure sensitive adhesive:
Composition and quality proportioning by phosphor-containing flame-proof acrylic acid pre-polymerization resin 100 parts by mass, outer addition type liquid flame retardant 5～20 parts by mass, curing agent 0.5～5 parts by mass, tackifying resin 1～10 parts by mass and ethyl acetate 10～50 parts by mass are got each component raw material;
Phosphor-containing flame-proof acrylic acid pre-polymerization resin is added mixing kettle; Stir with rotating speed 200～500rpm, add outer addition type liquid flame retardant under the room temperature gradually, stir 0.5-1h; Add curing agent, tackifying resin and ethyl acetate then successively; Stir 0.5h again, discharging makes the phosphor-containing flame-proof acrylate pressure sensitive adhesive;
A kind of among the Doher-601 that said outer addition type liquid flame retardant can be produced for Dongguan Dao Er chemical industry Co., Ltd, the ys-B014 that Nantong IELTS flame-retarded technology Co., Ltd produces or two kinds, both all belong to organic phosphorus flame retardant;
Said curing agent is one or more the mixture in epoxy resin, isocyanates, the melmac;
Said tackifying resin is one or both in rosin, the terpene resin;
C, preparation halogen-free antiflaming polyester label paper:
On coating machine; Using the steel wire scraper to be coated on thickness equably the phosphor-containing flame-proof acrylate pressure sensitive adhesive is that 0.025～0.100mm, width are on 500～5000mm halogen-free antiflaming polyester film; Gluing thickness is 0.015～0.050mm; Halogen-free antiflaming polyester film behind the gluing is with the linear velocity of 10～30m/min; Through total length 15～25m, the I section temperature passed through in order is that 65～75 ℃, II section temperature are that 85～95 ℃, III section temperature are that 105～115 ℃, IV section temperature are that 95～105 ℃ drying tunnel cures, and carries out further pre-polymerization and merges and remove the solvent in the phosphor-containing flame-proof acrylate pressure sensitive adhesive; And then halogen-free antiflaming polyester film and the thickness that will scribble polyacrylate pressure-sensitive be 0.025～0.05mm, width be 500～5000mm the polyester mould release membrance the pressure of pressure roller be 0.4MPa, temperature be carry out under the room temperature compound; Put into the slaking 48～72 hours again of 40～50 ℃ of drying rooms at last, promptly make the halogen-free antiflaming polyester label product.
In the content of the present invention: the monomer of phosphor-containing flame-proof described in the step a is preferably one or more the mixture in allyl dimethyl phosphate, allyl diethyl phosphate, (2-allyl phenoxy group) pentaphene oxygen basic ring three phosphonitriles.
In the content of the present invention: the said preparation halogen-free antiflaming polyester of step c label paper preferably replaces with: on coating machine; Using the steel wire scraper to be coated on thickness equably the phosphor-containing flame-proof acrylate pressure sensitive adhesive is that 0.025～0.100mm, width are on 500～5000mm halogen-free antiflaming polyester film; Gluing thickness is 0.015～0.050mm; Halogen-free antiflaming polyester film behind the gluing is with the linear velocity of 10～30m/min; Through total length 15～25m, the I section temperature passed through in order is that 70 ℃, II section temperature are that 90 ℃, III section temperature are that 110 ℃, IV section temperature are that 100 ℃ drying tunnel cures; And then halogen-free antiflaming polyester film and the thickness that will scribble polyacrylate pressure-sensitive be 0.025～0.05mm, width be 500～5000mm the polyester mould release membrance the pressure of pressure roller be 0.4MPa, temperature be carry out under the room temperature compound; Put into the slaking 72 hours again of 40～50 ℃ of drying rooms at last, promptly make the halogen-free antiflaming polyester label product.
In the content of the present invention: fire retardant mylar described in the step c (or claiming fire retardant mylar base material, basement membrane) is preferably VTM-0 grade non-halogen flame-retardant polyester film; Said fire retardant mylar can be white, black or clear films.
In the content of the present invention: the mould release membrance of polyester described in the step c is the commercially available common release polyester film at surface coated one deck mould release; The main protection halogen-free flameproof label glue-line that plays a part, be easy to when being convenient to the label use with the halogen-free flameproof film on coated face peel off.
The product of halogen-free antiflaming polyester label paper described in the step c of content of the present invention is promptly formed by three layers: ground floor is that mould release membrance, the second layer are that phosphor-containing flame-proof acrylate pressure sensitive adhesive (being phosphor-containing flame-proof acrylic pressure sensitive gel coating), the 3rd layer are basement membrane---halogen-free antiflaming polyester film.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) adopts the present invention; The phosphor-containing flame-proof acrylate pressure sensitive adhesive is through phosphor-containing flame-proof monomer and the synthetic phosphor-containing flame-proof acrylic acid pre-polymerization resin of acrylic ester monomer copolymerization; Thereby both introduced phosphonium flame retardant; Greatly reduce the use amount of outer additive flame retardant again, improved the fire resistance and the stability of phosphor-containing flame-proof acrylate pressure sensitive adhesive;
(2) the present invention is through adding curing agent and tackifying resin in phosphor-containing flame-proof acrylic acid pre-polymerization resin; Solve prior art and adopted the single solid to add fire retardant outward and the technical problem that causes pressure sensitive adhesive pressure-sensitive adhesive performance to decline to a great extent, strengthened the pressure-sensitive adhesive performance of phosphor-containing flame-proof acrylate pressure sensitive adhesive;
(3) the present invention is in the phosphor-containing flame-proof acrylate pressure sensitive adhesive; Adopted with the phosphor-containing flame-proof acrylate pressure sensitive adhesive in various compositions be prone to compatible outer addition type liquid flame retardant, solved prior art and used single solid flame retardant and glue compatibility bad and influence the difficult problem of product appearance;
(4) product of the present invention halogen-containing flame retardant not has eco-friendly characteristics, has eliminated the pollution of environment and the harm of human body;
(5) preparation technology of the present invention is easy, and fire resistance, pressure sensitive adhesive pressure-sensitive adhesive function admirable that label product is whole are practical.
Description of drawings
Fig. 1 is the section structure sketch map that adopts the halogen-free antiflaming polyester label paper of the present invention's preparation.
1-mould release membrance, 2-pressure sensitive adhesive, 3---basement membrane among the figure.
The specific embodiment
Embodiment given below intends so that the present invention is described further; But can not be interpreted as it is restriction to protection domain of the present invention; The technical staff in this field to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
First: preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin and preparation phosphor-containing flame-proof acrylate pressure sensitive adhesive (embodiment 1～5)
Embodiment 1:
1, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
(ethyl acetate: toluene=19:1), 0.5Kg benzoyl peroxide add the agitated reactor that has condensation reflux unit with 20Kg butyl acrylate, 45Kg Isooctyl acrylate monomer, 3Kg acrylic acid, 2Kg hydroxy-ethyl acrylate, 10Kg EMA, 20Kg phosphor-containing flame-proof monomer (2-allyl phenoxy group) pentaphene oxygen basic ring three phosphonitriles, 100Kg solvent under the room temperature; Condenser temperature is controlled at below 15 ℃; Stir with revolution 200rpm, mix; Under nitrogen protection, be warming up to 80 ℃ gradually, carry out solution copolymerization reaction 4h, stop heating, reaction finishes.
In addition: add 100Kg ethyl acetate again and mix, be cooled to the room temperature discharging, make phosphorous acrylic acid pre-polymerization resin (A), make solid content reach 33% subsequent use.
2, the preparation of phosphor-containing flame-proof acrylate pressure sensitive adhesive:
(1) prescription (unit: parts by mass can be Kg)
The phosphor-containing flame-proof acrylic acid pre-polymerization resin of above-mentioned formula ratio is added mixing kettle; Open stirring with rotating speed 200rpm, add the outer addition type liquid flame retardant of formula ratio under the room temperature gradually, mixing time 0.5h; The curing agent, tackifying resin and the ethyl acetate that add formula ratio then successively; Stir 0.5h again, discharging obtains the phosphor-containing flame-proof acrylate pressure sensitive adhesive.
Embodiment 2:
1, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
(ethyl acetate: toluene=19:1), 0.5Kg benzoyl peroxide add the agitated reactor that has condensation reflux unit with 50Kg butyl acrylate, 15Kg Isooctyl acrylate monomer, 3Kg acrylic acid, 2Kg hydroxy-ethyl acrylate, 10Kg EMA, 20Kg phosphor-containing flame-proof monomer allyl diethyl phosphate, 100Kg solvent under the room temperature; Condenser temperature is controlled at below 15 ℃; Stir with revolution 200rpm, mix; Under nitrogen protection, be warming up to 80 ℃ gradually, carry out solution copolymerization reaction 4h, stop heating, reaction finishes.
In addition: add 100Kg ethyl acetate again and mix, be cooled to the room temperature discharging, make phosphorous acrylic acid pre-polymerization resin (B), make solid content reach 33% subsequent use.
2, the preparation of phosphor-containing flame-proof acrylate pressure sensitive adhesive:
(1) prescription (unit: parts by mass can be Kg)
The phosphor-containing flame-proof acrylic acid pre-polymerization resin of above-mentioned formula ratio is added mixing kettle; Open stirring with rotating speed 200rpm, add the outer addition type liquid flame retardant of formula ratio under the room temperature gradually, mixing time 0.5h; The curing agent, tackifying resin and the ethyl acetate that add formula ratio then successively; Stir 0.5h again, discharging obtains the phosphor-containing flame-proof acrylate pressure sensitive adhesive.
Embodiment 3:
1, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
(ethyl acetate: toluene=19:1), 1.0Kg azo-bis-isobutyl cyanide add the agitated reactor that has condensation reflux unit with 30Kg butyl acrylate, 40Kg Isooctyl acrylate monomer, 6Kg acrylic acid, 4Kg hydroxy-ethyl acrylate, 10Kg EMA, 10Kg phosphor-containing flame-proof monomer (2-allyl phenoxy group) pentaphene oxygen basic ring three phosphonitriles, 100Kg solvent under the room temperature; Condenser temperature is controlled at below 15 ℃; Stir with revolution 200rpm, mix; Under nitrogen protection, be warming up to 80 ℃ gradually, carry out solution copolymerization reaction 4h, stop heating, reaction finishes.
In addition: add 100Kg ethyl acetate again and mix, be cooled to the room temperature discharging, make phosphorous acrylic acid pre-polymerization resin (C), make solid content reach 33% subsequent use.
2, the preparation of phosphor-containing flame-proof acrylate pressure sensitive adhesive:
(1) prescription (unit: parts by mass can be Kg)
The phosphor-containing flame-proof acrylic acid pre-polymerization resin of above-mentioned formula ratio is added mixing kettle; Open stirring with rotating speed 200rpm, add the outer addition type liquid flame retardant of formula ratio under the room temperature gradually, mixing time 0.5h; The curing agent, tackifying resin and the ethyl acetate that add formula ratio then successively; Stir 0.5h again, discharging obtains the phosphor-containing flame-proof acrylate pressure sensitive adhesive.
Embodiment 4:
1, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
(ethyl acetate: toluene=19:1), 2.0Kg azo-bis-isobutyl cyanide add the agitated reactor that has condensation reflux unit with 20Kg butyl acrylate, 55Kg Isooctyl acrylate monomer, 6Kg acrylic acid, 4Kg hydroxy-ethyl acrylate, 5Kg EMA, 10Kg phosphor-containing flame-proof monomer allyl dimethyl phosphate, 100Kg solvent under the room temperature; Condenser temperature is controlled at below 15 ℃; Open stirring with revolution 200rpm, mix; Under nitrogen protection, be warming up to 80 ℃ gradually, carry out solution copolymerization reaction 4h, stop heating, reaction finishes.
In addition: add 100Kg ethyl acetate again and mix, be cooled to the room temperature discharging, make phosphorous acrylic acid pre-polymerization resin (D), make solid content reach 33% subsequent use.
2, the preparation of phosphor-containing flame-proof acrylate pressure sensitive adhesive:
(1) prescription (unit: parts by mass can be Kg)
The phosphor-containing flame-proof acrylic acid pre-polymerization resin of above-mentioned formula ratio is added mixing kettle; Open stirring with rotating speed 200rpm, add the outer addition type liquid flame retardant of formula ratio under the room temperature gradually, mixing time 0.5h; The curing agent, tackifying resin and the ethyl acetate that add formula ratio then successively; Stir 0.5h again, discharging obtains the phosphor-containing flame-proof acrylate pressure sensitive adhesive.
Embodiment 5:
1, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
(ethyl acetate: toluene=19:1), 0.8Kg benzoyl peroxide add the agitated reactor that has condensation reflux unit with 30Kg butyl acrylate, 20Kg Isooctyl acrylate monomer, 6Kg acrylic acid, 4Kg hydroxy-ethyl acrylate, 10Kg EMA, 30Kg phosphor-containing flame-proof monomer [(2-allyl phenoxy group) pentaphene oxygen basic ring three phosphonitriles: allyl diethyl phosphate=2:1], 100Kg solvent under the room temperature; Condenser temperature is controlled at below 15 ℃; Open stirring with revolution 200rpm, mix; Under nitrogen protection, be warming up to 80 ℃ gradually, carry out solution copolymerization reaction 4h, stop heating, reaction finishes.
In addition: add 100Kg ethyl acetate again and mix, be cooled to the room temperature discharging, make phosphorous acrylic acid pre-polymerization resin (E), make solid content reach 33% subsequent use.
2, the preparation of phosphor-containing flame-proof acrylate pressure sensitive adhesive:
(1) prescription (unit: parts by mass can be Kg)
The phosphor-containing flame-proof acrylic acid pre-polymerization resin of above-mentioned formula ratio is added mixing kettle; Open stirring with rotating speed 200rpm, add the outer addition type liquid flame retardant of formula ratio under the room temperature gradually, mixing time 0.5h; The curing agent, tackifying resin and the ethyl acetate that add formula ratio then successively; Stir 0.5h again, discharging obtains the phosphor-containing flame-proof acrylate pressure sensitive adhesive.
Second portion: preparation VTM-0 grade non-halogen flame-retardant polyester label paper (embodiment 6～25)
On coating machine; Use the steel wire scraper to be coated on thickness equably the phosphor-containing flame-proof acrylate pressure sensitive adhesive as on 0.05mm, the VTM-0 level fire retardant mylar of width as 1000mm; Gluing thickness is 0.025mm; Halogen-free antiflaming polyester film behind the gluing is the linear velocity of 20m/min; Through length 25m, I section temperature is that 70 ℃, II section temperature are that 90 ℃, III section temperature are that 110 ℃, IV section temperature are that 100 ℃ drying tunnel cures, and carries out further pre-polymerization and merges and remove the solvent in the phosphor-containing flame-proof acrylate pressure sensitive adhesive; And then film and the thickness that will scribble polyacrylate pressure-sensitive be 0.025mm, width be 1000mm the polyester mould release membrance the pressure of pressure roller be 0.4MPa, temperature be carry out under the room temperature compound; Put into the slaking 72 hours again of 50 ℃ of drying rooms at last, obtain VTM-0 grade non-halogen flame-retardant polyester label product.Embodiment 6～25 bond propertiess and fire resistance see the following form.
Fire-retardant label bond properties and fire resistance test chart
Embodiment 26:
The preparation method of halogen-free antiflaming polyester label paper comprises the following steps:
A, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
(unit can be Kg with 45 parts by mass under the room temperature; Afterwards together) butyl acrylate, 35 parts by mass Isooctyl acrylate monomers, 5 parts by mass acrylic acid, 3.5 parts by mass hydroxy-ethyl acrylates, 12 parts by mass EMAs, 20 parts by mass phosphor-containing flame-proof monomers, 100 parts by mass solvents and 1.0 parts by mass initators join in the agitated reactor that has condensation reflux unit; Condenser temperature is controlled at below 15 ℃; Stir with revolution 200rpm, mix; Under nitrogen protection, be warming up to 75～80 ℃ gradually, carry out copolyreaction 5h, stop heating; Add an amount of solvent more evenly and make the mass percentage content of solids reach 33%, be cooled to room temperature, make phosphorous acrylic acid pre-polymerization resin, subsequent use;
Said phosphor-containing flame-proof monomer is the compound that contains two keys and bound phosphate groups;
Said solvent is a kind of in ethyl acetate, the toluene or two kinds;
Said initator is a kind of in benzoyl peroxide, the azo-bis-isobutyl cyanide or two kinds;
B, preparation phosphor-containing flame-proof acrylate pressure sensitive adhesive:
Press the composition and the quality proportioning of phosphor-containing flame-proof acrylic acid pre-polymerization resin 100 parts by mass (unit can be Kg, and the back together), outer addition type liquid flame retardant 12 parts by mass, curing agent 2.7 parts by mass, tackifying resin 5.5 parts by mass and ethyl acetate 30 parts by mass and get each component raw material;
Phosphor-containing flame-proof acrylic acid pre-polymerization resin is added mixing kettle, stir, add outer addition type liquid flame retardant under the room temperature gradually with rotating speed 350rpm; Stir 0.7h, add curing agent, tackifying resin and ethyl acetate then successively, stir 0.5h again; Discharging makes the phosphor-containing flame-proof acrylate pressure sensitive adhesive;
A kind of among the ys-B014 that said outer addition type liquid flame retardant is the Doher-601 that produces of Dongguan Dao Er chemical industry Co., Ltd, Nantong IELTS flame-retarded technology Co., Ltd produces or two kinds, both all belong to organic phosphorus flame retardant;
Said curing agent is one or more the mixture in epoxy resin, isocyanates, the melmac;
Said tackifying resin is one or both in rosin, the terpene resin;
C, preparation halogen-free antiflaming polyester label paper:
On coating machine; With the phosphor-containing flame-proof acrylate pressure sensitive adhesive use the steel wire scraper be coated on equably thickness as 0.055mm, width as on the 2500mm halogen-free antiflaming polyester film; Gluing thickness is 0.025mm; Halogen-free antiflaming polyester film behind the gluing is with the linear velocity of 20m/min; Through total length 20m, the I section temperature passed through in order is that 70 ℃, II section temperature are that 90 ℃, III section temperature are that 110 ℃, IV section temperature are that 100 ℃ drying tunnel cures, and carries out further pre-polymerization and merges and remove the solvent in the phosphor-containing flame-proof acrylate pressure sensitive adhesive; And then halogen-free antiflaming polyester film and the thickness that will scribble polyacrylate pressure-sensitive be 0.035mm, width be 2500mm the polyester mould release membrance the pressure of pressure roller be 0.4MPa, temperature be carry out under the room temperature compound; Put into the slaking 72 hours again of 40～50 ℃ of drying rooms at last, promptly make the halogen-free antiflaming polyester label product.
Embodiment 27:
The preparation method of halogen-free antiflaming polyester label paper comprises the following steps:
A, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
(unit can be Kg with 20 parts by mass under the room temperature; Afterwards together) butyl acrylate, 15 parts by mass Isooctyl acrylate monomers, 3 parts by mass acrylic acid, 2 parts by mass hydroxy-ethyl acrylates, 5 parts by mass EMAs, 10 parts by mass phosphor-containing flame-proof monomers, 50 parts by mass solvents and 0.1 parts by mass initator join in the agitated reactor that has condensation reflux unit; Condenser temperature is controlled at below 15 ℃; Stir with revolution 100rpm, mix; Under nitrogen protection, be warming up to 75～80 ℃ gradually, carry out copolyreaction 4h, stop heating; Add an amount of solvent more evenly and make the mass percentage content of solids reach 33%, be cooled to room temperature, make phosphorous acrylic acid pre-polymerization resin, subsequent use;
Said phosphor-containing flame-proof monomer is the compound that contains two keys and bound phosphate groups;
Said solvent is a kind of in ethyl acetate, the toluene or two kinds;
Said initator is a kind of in benzoyl peroxide, the azo-bis-isobutyl cyanide or two kinds;
B, preparation phosphor-containing flame-proof acrylate pressure sensitive adhesive:
Press the composition and the quality proportioning of phosphor-containing flame-proof acrylic acid pre-polymerization resin 100 parts by mass (unit can be Kg, and the back together), outer addition type liquid flame retardant 5 parts by mass, curing agent 0.5 parts by mass, tackifying resin 1 parts by mass and ethyl acetate 10 parts by mass and get each component raw material;
Phosphor-containing flame-proof acrylic acid pre-polymerization resin is added mixing kettle, stir, add outer addition type liquid flame retardant under the room temperature gradually with rotating speed 200rpm; Stir 0.5h, add curing agent, tackifying resin and ethyl acetate then successively, stir 0.5h again; Discharging makes the phosphor-containing flame-proof acrylate pressure sensitive adhesive;
A kind of among the ys-B014 that said outer addition type liquid flame retardant is the Doher-601 that produces of Dongguan Dao Er chemical industry Co., Ltd, Nantong IELTS flame-retarded technology Co., Ltd produces or two kinds, both all belong to organic phosphorus flame retardant;
Said curing agent is one or more the mixture in epoxy resin, isocyanates, the melmac;
Said tackifying resin is one or both in rosin, the terpene resin;
C, preparation halogen-free antiflaming polyester label paper:
On coating machine; With the phosphor-containing flame-proof acrylate pressure sensitive adhesive use the steel wire scraper be coated on equably thickness as 0.025mm, width as on the 500mm halogen-free antiflaming polyester film; Gluing thickness is 0.015mm; Halogen-free antiflaming polyester film behind the gluing is with the linear velocity of 10m/min; Through total length 15m, the I section temperature passed through in order is that 70 ℃, II section temperature are that 90 ℃, III section temperature are that 110 ℃, IV section temperature are that 100 ℃ drying tunnel cures, and carries out further pre-polymerization and merges and remove the solvent in the phosphor-containing flame-proof acrylate pressure sensitive adhesive; And then halogen-free antiflaming polyester film and the thickness that will scribble polyacrylate pressure-sensitive be 0.025mm, width be 500mm the polyester mould release membrance the pressure of pressure roller be 0.4MPa, temperature be carry out under the room temperature compound; Put into the slaking 72 hours again of 40～50 ℃ of drying rooms at last, promptly make the halogen-free antiflaming polyester label product.
Embodiment 28:
The preparation method of halogen-free antiflaming polyester label paper comprises the following steps:
A, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
(unit can be Kg with 70 parts by mass under the room temperature; Afterwards together) butyl acrylate, 55 parts by mass Isooctyl acrylate monomers, 7 parts by mass acrylic acid, 5 parts by mass hydroxy-ethyl acrylates, 20 parts by mass EMAs, 30 parts by mass phosphor-containing flame-proof monomers, 150 parts by mass solvents and 2.0 parts by mass initators join in the agitated reactor that has condensation reflux unit; Condenser temperature is controlled at below 15 ℃; Stir with revolution 300rpm, mix; Under nitrogen protection, be warming up to 75～80 ℃ gradually, carry out copolyreaction 6h, stop heating; It is even and make the mass percentage content of solids reach 33% to add (in right amount) solvent again, is cooled to room temperature, makes phosphorous acrylic acid pre-polymerization resin, subsequent use;
Said phosphor-containing flame-proof monomer is the compound that contains two keys and bound phosphate groups;
Said solvent is a kind of in ethyl acetate, the toluene or two kinds;
Said initator is a kind of in benzoyl peroxide, the azo-bis-isobutyl cyanide or two kinds;
B, preparation phosphor-containing flame-proof acrylate pressure sensitive adhesive:
Press the composition and the quality proportioning of phosphor-containing flame-proof acrylic acid pre-polymerization resin 100 parts by mass (unit can be Kg, and the back together), outer addition type liquid flame retardant 20 parts by mass, curing agent 5 parts by mass, tackifying resin 10 parts by mass and ethyl acetate 50 parts by mass and get each component raw material;
Phosphor-containing flame-proof acrylic acid pre-polymerization resin is added mixing kettle, stir, add outer addition type liquid flame retardant under the room temperature gradually with rotating speed 500rpm; Stir 1h, add curing agent, tackifying resin and ethyl acetate then successively, stir 0.5h again; Discharging makes the phosphor-containing flame-proof acrylate pressure sensitive adhesive;
A kind of among the ys-B014 that said outer addition type liquid flame retardant is the Doher-601 that produces of Dongguan Dao Er chemical industry Co., Ltd, Nantong IELTS flame-retarded technology Co., Ltd produces or two kinds, both all belong to organic phosphorus flame retardant;
Said curing agent is one or more the mixture in epoxy resin, isocyanates, the melmac;
Said tackifying resin is one or both in rosin, the terpene resin;
C, preparation halogen-free antiflaming polyester label paper:
On coating machine; With the phosphor-containing flame-proof acrylate pressure sensitive adhesive use the steel wire scraper be coated on equably thickness as 0.100mm, width as on the 5000mm halogen-free antiflaming polyester film; Gluing thickness is 0.050mm; Halogen-free antiflaming polyester film behind the gluing is with the linear velocity of 30m/min; Through total length 25m, the I section temperature passed through in order is that 70 ℃, II section temperature are that 90 ℃, III section temperature are that 110 ℃, IV section temperature are that 100 ℃ drying tunnel cures, and carries out further pre-polymerization and merges and remove the solvent in the phosphor-containing flame-proof acrylate pressure sensitive adhesive; And then halogen-free antiflaming polyester film and the thickness that will scribble polyacrylate pressure-sensitive be 0.05mm, width be 5000mm the polyester mould release membrance the pressure of pressure roller be 0.4MPa, temperature be carry out under the room temperature compound; Put into the slaking 72 hours again of 40～50 ℃ of drying rooms at last, promptly make the halogen-free antiflaming polyester label product.
Embodiment 29:
The preparation method of halogen-free antiflaming polyester label paper comprises the following steps:
A, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
(unit can be Kg with 20～70 parts by mass under the room temperature; Afterwards together) butyl acrylate, 15～55 parts by mass Isooctyl acrylate monomers, 3～7 parts by mass acrylic acid, 2～5 parts by mass hydroxy-ethyl acrylates, 5～20 parts by mass EMAs, 10-30 parts by mass phosphor-containing flame-proof monomer, 50～150 parts by mass solvents and 0.1～2.0 parts by mass initator join in the agitated reactor that has condensation reflux unit; Condenser temperature is controlled at below 15 ℃; Stir with revolution 100～300rpm, mix; Under nitrogen protection, be warming up to 75～80 ℃ gradually, carry out copolyreaction 4～6h, stop heating; Add an amount of solvent more evenly and make the mass percentage content of solids reach 33%, be cooled to room temperature, make phosphorous acrylic acid pre-polymerization resin, subsequent use;
Said phosphor-containing flame-proof monomer is the compound that contains two keys and bound phosphate groups;
Said solvent is a kind of in ethyl acetate, the toluene or two kinds;
Said initator is a kind of in benzoyl peroxide, the azo-bis-isobutyl cyanide or two kinds;
B, preparation phosphor-containing flame-proof acrylate pressure sensitive adhesive:
Press the composition and the quality proportioning of phosphor-containing flame-proof acrylic acid pre-polymerization resin 100 parts by mass (unit can be Kg, and the back together), outer addition type liquid flame retardant 5～20 parts by mass, curing agent 0.5～5 parts by mass, tackifying resin 1～10 parts by mass and ethyl acetate 10～50 parts by mass and get each component raw material;
Phosphor-containing flame-proof acrylic acid pre-polymerization resin is added mixing kettle; Stir with rotating speed 200～500rpm, add outer addition type liquid flame retardant under the room temperature gradually, stir 0.5～1h; Add curing agent, tackifying resin and ethyl acetate then successively; Stir 0.5h again, discharging makes the phosphor-containing flame-proof acrylate pressure sensitive adhesive;
A kind of among the ys-B014 that said outer addition type liquid flame retardant is the Doher-601 that produces of Dongguan Dao Er chemical industry Co., Ltd, Nantong IELTS flame-retarded technology Co., Ltd produces or two kinds, both all belong to organic phosphorus flame retardant;
Said curing agent is one or more the mixture in epoxy resin, isocyanates, the melmac;
Said tackifying resin is one or both in rosin, the terpene resin;
C, preparation halogen-free antiflaming polyester label paper:
On coating machine; Using the steel wire scraper to be coated on thickness equably the phosphor-containing flame-proof acrylate pressure sensitive adhesive is that 0.025～0.100mm, width are on 500～5000mm halogen-free antiflaming polyester film; Gluing thickness is 0.015～0.050mm; Halogen-free antiflaming polyester film behind the gluing is with the linear velocity of 10～30m/min; Through total length 15～25m, the I section temperature passed through in order is that 70 ℃, II section temperature are that 90 ℃, III section temperature are that 110 ℃, IV section temperature are that 100 ℃ drying tunnel cures, and carries out further pre-polymerization and merges and remove the solvent in the phosphor-containing flame-proof acrylate pressure sensitive adhesive; And then halogen-free antiflaming polyester film and the thickness that will scribble polyacrylate pressure-sensitive be 0.025～0.05mm, width be 500～5000mm the polyester mould release membrance the pressure of pressure roller be 0.4MPa, temperature be carry out under the room temperature compound; Put into the slaking 72 hours again of 40～50 ℃ of drying rooms at last, promptly make the halogen-free antiflaming polyester label product.
Embodiment 30-36:
The preparation method of halogen-free antiflaming polyester label paper comprises the following steps:
A, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
(unit can be Kg with 20～70 parts by mass under the room temperature; Afterwards together) butyl acrylate, 15～55 parts by mass Isooctyl acrylate monomers, 3～7 parts by mass acrylic acid, 2～5 parts by mass hydroxy-ethyl acrylates, 5～20 parts by mass EMAs, 10～30 parts by mass phosphor-containing flame-proof monomers, 50～150 parts by mass solvents and 0.1～2.0 parts by mass initator join in the agitated reactor that has condensation reflux unit; Condenser temperature is controlled at below 15 ℃; Stir with revolution 100～300rpm, mix; Under nitrogen protection, be warming up to 75～80 ℃ gradually, carry out copolyreaction 4～6h, stop heating; Add an amount of solvent more evenly and make the mass percentage content of solids reach 33%, be cooled to room temperature, make phosphorous acrylic acid pre-polymerization resin, subsequent use; The concrete parts by mass consumption of each raw material components sees the following form among each embodiment:
Said phosphor-containing flame-proof monomer is the compound that contains two keys and bound phosphate groups;
Said solvent is a kind of in ethyl acetate, the toluene or two kinds;
Said initator is a kind of in benzoyl peroxide, the azo-bis-isobutyl cyanide or two kinds;
B, preparation phosphor-containing flame-proof acrylate pressure sensitive adhesive:
Press the composition and the quality proportioning of phosphor-containing flame-proof acrylic acid pre-polymerization resin 100 parts by mass (unit can be Kg, and the back together), outer addition type liquid flame retardant 5～20 parts by mass, curing agent 0.5～5 parts by mass, tackifying resin 1～10 parts by mass and ethyl acetate 10～50 parts by mass and get each component raw material; The concrete parts by mass consumption of each component raw material sees the following form among each embodiment:
Phosphor-containing flame-proof acrylic acid pre-polymerization resin is added mixing kettle; Stir with rotating speed 200～500rpm, add outer addition type liquid flame retardant under the room temperature gradually, stir 0.5～1h; Add curing agent, tackifying resin and ethyl acetate then successively; Stir 0.5h again, discharging makes the phosphor-containing flame-proof acrylate pressure sensitive adhesive;
A kind of among the ys-B014 that said outer addition type liquid flame retardant is the Doher-601 that produces of Dongguan Dao Er chemical industry Co., Ltd, Nantong IELTS flame-retarded technology Co., Ltd produces or two kinds, both all belong to organic phosphorus flame retardant;
Said curing agent is one or more the mixture in epoxy resin, isocyanates, the melmac;
Said tackifying resin is one or both in rosin, the terpene resin;
C, preparation halogen-free antiflaming polyester label paper:
On coating machine; Using the steel wire scraper to be coated on thickness equably the phosphor-containing flame-proof acrylate pressure sensitive adhesive is that 0.025～0.100mm, width are on 500～5000mm halogen-free antiflaming polyester film; Gluing thickness is 0.015～0.050mm; Halogen-free antiflaming polyester film behind the gluing is with the linear velocity of 10～30m/min; Through total length 15～25m, the I section temperature passed through in order is that 70 ℃, II section temperature are that 90 ℃, III section temperature are that 110 ℃, IV section temperature are that 100 ℃ drying tunnel cures, and carries out further pre-polymerization and merges and remove the solvent in the phosphor-containing flame-proof acrylate pressure sensitive adhesive; And then halogen-free antiflaming polyester film and the thickness that will scribble polyacrylate pressure-sensitive be 0.025～0.05mm, width be 500～5000mm the polyester mould release membrance the pressure of pressure roller be 0.4MPa, temperature be carry out under the room temperature compound; Put into the slaking 72 hours again of 40～50 ℃ of drying rooms at last, promptly make the halogen-free antiflaming polyester label product.
Embodiment 37:
The preparation method of halogen-free antiflaming polyester label paper comprises the following steps:
A, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
Under the room temperature 40 parts by mass butyl acrylates, 40 parts by mass Isooctyl acrylate monomers, 6 parts by mass acrylic acid, 4 parts by mass hydroxy-ethyl acrylates, 13 parts by mass EMAs, 21 parts by mass phosphor-containing flame-proof monomers, 130 parts by mass solvents and 1.2 parts by mass initators are joined in the agitated reactor that has condensation reflux unit; Condenser temperature is controlled at below 15 ℃; Stir with revolution 100～300rpm, mix; Under nitrogen protection, be warming up to 75～80 ℃ gradually, carry out copolyreaction 4～6h, stop heating; Add solvent more evenly and make the mass percentage content of solids reach 32%, be cooled to room temperature, make phosphorous acrylic acid pre-polymerization resin, subsequent use;
Said phosphor-containing flame-proof monomer is the compound that contains two keys and bound phosphate groups;
Said solvent is a kind of in ethyl acetate, the toluene or two kinds;
Said initator is a kind of in benzoyl peroxide, the azo-bis-isobutyl cyanide or two kinds;
B, preparation phosphor-containing flame-proof acrylate pressure sensitive adhesive:
Composition and quality proportioning by phosphor-containing flame-proof acrylic acid pre-polymerization resin 100 parts by mass, outer addition type liquid flame retardant 13 parts by mass, curing agent 3 parts by mass, tackifying resin 6 parts by mass and ethyl acetate 32 parts by mass are got each component raw material;
Phosphor-containing flame-proof acrylic acid pre-polymerization resin is added mixing kettle; Stir with rotating speed 200～500rpm, add outer addition type liquid flame retardant under the room temperature gradually, stir 0.8h; Add curing agent, tackifying resin and ethyl acetate then successively; Stir 0.5h again, discharging makes the phosphor-containing flame-proof acrylate pressure sensitive adhesive;
A kind of among the ys-B014 that said outer addition type liquid flame retardant is the Doher-601 that produces of Dongguan Dao Er chemical industry Co., Ltd, Nantong IELTS flame-retarded technology Co., Ltd produces or two kinds;
Said curing agent is one or more the mixture in epoxy resin, isocyanates, the melmac;
Said tackifying resin is one or both in rosin, the terpene resin;
C, preparation halogen-free antiflaming polyester label paper:
On coating machine; With the phosphor-containing flame-proof acrylate pressure sensitive adhesive use the steel wire scraper be coated on equably thickness as 0.075mm, width as on the 3500mm halogen-free antiflaming polyester film; Gluing thickness is 0.025mm; Halogen-free antiflaming polyester film behind the gluing is with the linear velocity of 23m/min; Through total length 22m, the I section temperature passed through in order is that 65～75 ℃, II section temperature are that 85～95 ℃, III section temperature are that 105～115 ℃, IV section temperature are that 95～105 ℃ drying tunnel cures; And then halogen-free antiflaming polyester film and the thickness that will scribble polyacrylate pressure-sensitive is that 0.045mm, width are that the polyester mould release membrance of 3500mm is that 0.4MPa, temperature are to carry out compoundly under the room temperature at the pressure of pressure roller, puts into the slaking 60 hours again of 40～50 ℃ of drying rooms at last, promptly makes the halogen-free antiflaming polyester label product.
Embodiment 38:
The preparation method of halogen-free antiflaming polyester label paper comprises the following steps:
A, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
Under the room temperature 20 parts by mass butyl acrylates, 20 parts by mass Isooctyl acrylate monomers, 4 parts by mass acrylic acid, 3 parts by mass hydroxy-ethyl acrylates, 7 parts by mass EMAs, 12 parts by mass phosphor-containing flame-proof monomers, 80 parts by mass solvents and 0.2 parts by mass initator are joined in the agitated reactor that has condensation reflux unit; Condenser temperature is controlled at below 15 ℃; Stir with revolution 150rpm, mix; Under nitrogen protection, be warming up to 75～80 ℃ gradually, carry out copolyreaction 4.5h, stop heating; Add solvent more evenly and make the mass percentage content of solids reach 30%, be cooled to room temperature, make phosphorous acrylic acid pre-polymerization resin, subsequent use;
Said phosphor-containing flame-proof monomer is the compound that contains two keys and bound phosphate groups;
Said solvent is a kind of in ethyl acetate, the toluene or two kinds;
Said initator is a kind of in benzoyl peroxide, the azo-bis-isobutyl cyanide or two kinds;
B, preparation phosphor-containing flame-proof acrylate pressure sensitive adhesive:
Composition and quality proportioning by phosphor-containing flame-proof acrylic acid pre-polymerization resin 100 parts by mass, outer addition type liquid flame retardant 7 parts by mass, curing agent 1.5 parts by mass, tackifying resin 2 parts by mass and ethyl acetate 18 parts by mass are got each component raw material;
Phosphor-containing flame-proof acrylic acid pre-polymerization resin is added mixing kettle, stir, add outer addition type liquid flame retardant under the room temperature gradually with rotating speed 250rpm; Stir 0.5h, add curing agent, tackifying resin and ethyl acetate then successively, stir 0.5h again; Discharging makes the phosphor-containing flame-proof acrylate pressure sensitive adhesive;
A kind of among the ys-B014 that said outer addition type liquid flame retardant is the Doher-601 that produces of Dongguan Dao Er chemical industry Co., Ltd, Nantong IELTS flame-retarded technology Co., Ltd produces or two kinds;
Said curing agent is one or more the mixture in epoxy resin, isocyanates, the melmac;
Said tackifying resin is one or both in rosin, the terpene resin;
C, preparation halogen-free antiflaming polyester label paper:
On coating machine; With the phosphor-containing flame-proof acrylate pressure sensitive adhesive use the steel wire scraper be coated on equably thickness as 0.030mm, width as on the 800mm halogen-free antiflaming polyester film; Gluing thickness is 0.020mm; Halogen-free antiflaming polyester film behind the gluing is with the linear velocity of 15m/min; Through total length 18m, the I section temperature passed through in order is that 65～75 ℃, II section temperature are that 85～95 ℃, III section temperature are that 105～115 ℃, IV section temperature are that 95～105 ℃ drying tunnel cures; And then halogen-free antiflaming polyester film and the thickness that will scribble polyacrylate pressure-sensitive is that 0.030mm, width are that the polyester mould release membrance of 800mm is that 0.4MPa, temperature are to carry out compoundly under the room temperature at the pressure of pressure roller, puts into the slaking 48 hours again of 40～50 ℃ of drying rooms at last, promptly makes the halogen-free antiflaming polyester label product.
Embodiment 39:
The preparation method of halogen-free antiflaming polyester label paper comprises the following steps:
A, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
Under the room temperature 70 parts by mass butyl acrylates, 50 parts by mass Isooctyl acrylate monomers, 6 parts by mass acrylic acid, 5 parts by mass hydroxy-ethyl acrylates, 18 parts by mass EMAs, 28 parts by mass phosphor-containing flame-proof monomers, 130 parts by mass solvents and 1.5 parts by mass initators are joined in the agitated reactor that has condensation reflux unit; Condenser temperature is controlled at below 15 ℃; Stir with revolution 250rpm, mix; Under nitrogen protection, be warming up to 75～80 ℃ gradually, carry out copolyreaction 5h, stop heating; Add solvent more evenly and make the mass percentage content of solids reach 32%, be cooled to room temperature, make phosphorous acrylic acid pre-polymerization resin, subsequent use;
Said phosphor-containing flame-proof monomer is the compound that contains two keys and bound phosphate groups;
Said solvent is a kind of in ethyl acetate, the toluene or two kinds;
Said initator is a kind of in benzoyl peroxide, the azo-bis-isobutyl cyanide or two kinds;
B, preparation phosphor-containing flame-proof acrylate pressure sensitive adhesive:
Composition and quality proportioning by phosphor-containing flame-proof acrylic acid pre-polymerization resin 100 parts by mass, outer addition type liquid flame retardant 18 parts by mass, curing agent 4 parts by mass, tackifying resin 9 parts by mass and ethyl acetate 40 parts by mass are got each component raw material;
Phosphor-containing flame-proof acrylic acid pre-polymerization resin is added mixing kettle, stir, add outer addition type liquid flame retardant under the room temperature gradually with rotating speed 250rpm; Stir 1h, add curing agent, tackifying resin and ethyl acetate then successively, stir 0.5h again; Discharging makes the phosphor-containing flame-proof acrylate pressure sensitive adhesive;
A kind of among the ys-B014 that said outer addition type liquid flame retardant is the Doher-601 that produces of Dongguan Dao Er chemical industry Co., Ltd, Nantong IELTS flame-retarded technology Co., Ltd produces or two kinds;
Said curing agent is one or more the mixture in epoxy resin, isocyanates, the melmac;
Said tackifying resin is one or both in rosin, the terpene resin;
C, preparation halogen-free antiflaming polyester label paper:
On coating machine; With the phosphor-containing flame-proof acrylate pressure sensitive adhesive use the steel wire scraper be coated on equably thickness as 0.090mm, width as on the 4000mm halogen-free antiflaming polyester film; Gluing thickness is 0.045mm; Halogen-free antiflaming polyester film behind the gluing is with the linear velocity of 25m/min; Through total length 23m, the I section temperature passed through in order is that 65～75 ℃, II section temperature are that 85～95 ℃, III section temperature are that 105～115 ℃, IV section temperature are that 95～105 ℃ drying tunnel cures; And then halogen-free antiflaming polyester film and the thickness that will scribble polyacrylate pressure-sensitive is that 0.045mm, width are that the polyester mould release membrance of 4000mm is that 0.4MPa, temperature are to carry out compoundly under the room temperature at the pressure of pressure roller, puts into the slaking 72 hours again of 40～50 ℃ of drying rooms at last, promptly makes the halogen-free antiflaming polyester label product.
In the foregoing description 26-39: the mixture of one or more in the preferred allyl dimethyl phosphate of the monomer of phosphor-containing flame-proof described in the step a, allyl diethyl phosphate, (2-allyl phenoxy group) pentaphene oxygen basic ring three phosphonitriles.
In the foregoing description 26-39: fire retardant mylar described in the step c (or claiming fire retardant mylar base material, basement membrane) is preferably VTM-0 grade non-halogen flame-retardant polyester film; Said fire retardant mylar can be white, black or transparent.
In the foregoing description 26-39: the mould release membrance of polyester described in the step c is the commercially available common release polyester film at surface coated one deck mould release.
In the foregoing description 26-39: the label paper of halogen-free antiflaming polyester described in step c product is formed by three layers, and ground floor is that mould release membrance, the second layer are that phosphor-containing flame-proof acrylate pressure sensitive adhesive (coating), the 3rd layer are basement membrane---halogen-free antiflaming polyester film.
In the foregoing description: each raw material that is adopted is the commercially available prod.A kind of among the ys-B014 that said outer addition type liquid flame retardant is the Doher-601 that produces of Dongguan Dao Er chemical industry Co., Ltd, Nantong IELTS flame-retarded technology Co., Ltd produces or two kinds, both all belong to organic phosphorus flame retardant.
In content of the present invention and the foregoing description, fire-retardant label bond properties and fire resistance method of testing and equipment are: tack: according to GB/T 4852-2002 standard, (precious big Instr Ltd.) measures with PT-6030 type tack tester; Hold viscosity:, hold sticking type tester (precious big Instr Ltd.) with the PT-6012 type and measure according to GB/T 4851-1998 standard; Peel strength under 180 ℃ of conditions: according to GB/T 2792-1998 standard, (precious big Instr Ltd.) measures with PT-6086PC type electron detachment machine; Fire resistance: according to the UL-94 standard, (the towering like a mountain peak tester Co., Ltd of Kunshan sun) measures with 5402 types level-testing vertical flammability machine.
In the foregoing description: in the percentage that is adopted, do not indicate especially, be the mass percent example; Said parts by mass can all be gram or kilogram.
In the foregoing description: the technological parameter in each step (temperature, time, concentration etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.
The not concrete same prior art of narrating of technology contents in content of the present invention and the foregoing description.
The invention is not restricted to the foregoing description, content of the present invention is said all can implement and have said good result.
Claims (3)
1. the preparation method of halogen-free antiflaming polyester label paper is characterized in that comprising the following steps:
A, preparation phosphor-containing flame-proof acrylic acid pre-polymerization resin:
Under the room temperature 20～70 parts by mass butyl acrylates, 15～55 parts by mass Isooctyl acrylate monomers, 3～7 parts by mass acrylic acid, 2～5 parts by mass hydroxy-ethyl acrylates, 5～20 parts by mass EMAs, 10～30 parts by mass phosphor-containing flame-proof monomers, 50～150 parts by mass solvents and 0.1～2.0 parts by mass initator are joined in the agitated reactor that has condensation reflux unit; Condenser temperature is controlled at below 15 ℃; Stir with revolution 100～300rpm, mix; Under nitrogen protection, be warming up to 75～80 ℃ gradually, carry out copolyreaction 4～6h, stop heating; Add solvent more evenly and make the mass percentage content of solids reach 30%～33%, be cooled to room temperature, make phosphorous acrylic acid pre-polymerization resin, subsequent use;
Said phosphor-containing flame-proof monomer is the compound that contains two keys and bound phosphate groups;
Said solvent is a kind of in ethyl acetate, the toluene or two kinds;
Said initator is a kind of in benzoyl peroxide, the azo-bis-isobutyl cyanide or two kinds;
B, preparation phosphor-containing flame-proof acrylate pressure sensitive adhesive:
Composition and quality proportioning by phosphor-containing flame-proof acrylic acid pre-polymerization resin 100 parts by mass, outer addition type liquid flame retardant 5～20 parts by mass, curing agent 0.5～5 parts by mass, tackifying resin 1～10 parts by mass and ethyl acetate 10～50 parts by mass are got each component raw material;
Phosphor-containing flame-proof acrylic acid pre-polymerization resin is added mixing kettle; Stir with rotating speed 200～500rpm, add outer addition type liquid flame retardant under the room temperature gradually, stir 0.5～1h; Add curing agent, tackifying resin and ethyl acetate then successively; Stir 0.5h again, discharging makes the phosphor-containing flame-proof acrylate pressure sensitive adhesive;
A kind of among the ys-B014 that said outer addition type liquid flame retardant is the Doher-601 that produces of Dongguan Dao Er chemical industry Co., Ltd, Nantong IELTS flame-retarded technology Co., Ltd produces or two kinds;
Said curing agent is one or more the mixture in epoxy resin, isocyanates, the melmac;
Said tackifying resin is one or both in rosin, the terpene resin;
C, preparation halogen-free antiflaming polyester label paper:
On coating machine; Using the steel wire scraper to be coated on thickness equably the phosphor-containing flame-proof acrylate pressure sensitive adhesive is that 0.025～0.100mm, width are on 500～5000mm halogen-free antiflaming polyester film; Gluing thickness is 0.015～0.050mm; Halogen-free antiflaming polyester film behind the gluing is with the linear velocity of 10～30m/min; Through total length 15～25m, the I section temperature passed through in order is that 65～75 ℃, II section temperature are that 85～95 ℃, III section temperature are that 105～115 ℃, IV section temperature are that 95～105 ℃ drying tunnel cures; And then halogen-free antiflaming polyester film and the thickness that will scribble polyacrylate pressure-sensitive be 0.025～0.05mm, width be 500～5000mm the polyester mould release membrance the pressure of pressure roller be 0.4MPa, temperature be carry out under the room temperature compound; Put into the slaking 48～72 hours again of 40～50 ℃ of drying rooms at last, promptly make the halogen-free antiflaming polyester label product.
2. by the preparation method of the described halogen-free antiflaming polyester label paper of claim 1, it is characterized in that: the monomer of phosphor-containing flame-proof described in the step a is one or more the mixture in allyl dimethyl phosphate, allyl diethyl phosphate, (2-allyl phenoxy group) pentaphene oxygen basic ring three phosphonitriles.
3. press the preparation method of the described halogen-free antiflaming polyester label paper of claim 1; It is characterized in that: the said preparation halogen-free antiflaming polyester of step c label paper replaces with: on coating machine; Using the steel wire scraper to be coated on thickness equably the phosphor-containing flame-proof acrylate pressure sensitive adhesive is that 0.025～0.100mm, width are on 500～5000mm halogen-free antiflaming polyester film; Gluing thickness is 0.015～0.050mm; Halogen-free antiflaming polyester film behind the gluing is with the linear velocity of 10～30m/min; Through total length 15～25m, the I section temperature passed through in order is that 70 ℃, II section temperature are that 90 ℃, III section temperature are that 110 ℃, IV section temperature are that 100 ℃ drying tunnel cures; And then halogen-free antiflaming polyester film and the thickness that will scribble polyacrylate pressure-sensitive is that 0.025～0.05mm, width are that the polyester mould release membrance of 500～5000mm is that 0.4MPa, temperature are to carry out compoundly under the room temperature at the pressure of pressure roller, puts into the slaking 72 hours again of 40～50 ℃ of drying rooms at last, promptly makes the halogen-free antiflaming polyester label product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110444349.0A CN102518003B (en) | 2011-12-27 | 2011-12-27 | Preparation method for halogen-free flame retardant polyester labeled paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110444349.0A CN102518003B (en) | 2011-12-27 | 2011-12-27 | Preparation method for halogen-free flame retardant polyester labeled paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102518003A true CN102518003A (en) | 2012-06-27 |
| CN102518003B CN102518003B (en) | 2014-03-26 |
Family
ID=46289047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110444349.0A Active CN102518003B (en) | 2011-12-27 | 2011-12-27 | Preparation method for halogen-free flame retardant polyester labeled paper |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102518003B (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941707A (en) * | 2012-11-01 | 2013-02-27 | 广州市金万正印刷材料有限公司 | Soft laser self-adhesive label film and preparation method thereof |
| CN103568456A (en) * | 2012-07-24 | 2014-02-12 | 苏州维艾普新材料有限公司 | Compounding technology by taking polyacrylic acid as adhesive |
| CN103834329A (en) * | 2014-03-18 | 2014-06-04 | 苏州斯迪克新材料科技股份有限公司 | Halogen-free environment-friendly adhesive and preparation method thereof |
| CN104099044A (en) * | 2013-04-02 | 2014-10-15 | 联冠(开平)胶粘制品有限公司 | Label adhesive for sticking on oil stain surface and preparation method thereof |
| CN105702155A (en) * | 2016-04-13 | 2016-06-22 | 广盟（广州）包装有限公司 | Composite label and production process thereof |
| CN106398596A (en) * | 2016-08-31 | 2017-02-15 | 潍坊恒彩数码影像材料有限公司 | Flame-retardant glue |
| WO2017153227A1 (en) * | 2016-03-10 | 2017-09-14 | Clariant Plastics & Coatings Ltd | Halogen-free, intumescent fire-proof coating, and use thereof |
| CN108285546A (en) * | 2018-03-01 | 2018-07-17 | 苏州维洛克电子科技有限公司 | A kind of fire retardant mylar and preparation method thereof of without phosphorus Halogen |
| CN108510874A (en) * | 2018-04-08 | 2018-09-07 | 深圳昌茂粘胶新材料有限公司 | Fire-retardant label of a kind of self-bleeding battery of environmental protection and preparation method thereof |
| CN108864976A (en) * | 2018-08-10 | 2018-11-23 | 阜南县力韦包装材料有限公司 | A kind of fire-retardant mightiness belt of waterproof antiwear |
| CN109294490A (en) * | 2018-10-14 | 2019-02-01 | 佛山市顺德区永创翔亿电子材料有限公司 | Battery flame-retardant adhesive and preparation method and battery single layer fire retardant insulating indigo plant film |
| CN109797603A (en) * | 2019-01-29 | 2019-05-24 | 上海万戈工贸发展有限公司 | One kind having waterproof low-smoke non-halogen flame-retardant paper and preparation method thereof |
| CN109852322A (en) * | 2018-12-04 | 2019-06-07 | 顺德职业技术学院 | Thermally conductive reaction-type flame-retarding polyurethane hot melt of one-component and preparation method thereof |
| CN109935159A (en) * | 2019-03-28 | 2019-06-25 | 深圳昌茂粘胶新材料有限公司 | A kind of reticulate pattern heat-conducting glue label material and preparation method thereof with flame retarding function |
| CN110144096A (en) * | 2019-06-03 | 2019-08-20 | 陕西科技大学 | A kind of flame-retardant polypropelene acid esters lotion and preparation method thereof |
| CN110407979A (en) * | 2019-08-09 | 2019-11-05 | 苏州高泰电子技术股份有限公司 | Pressure-sensitive gum resin and light transmission flame-retardant double sided tape comprising it |
| CN110628362A (en) * | 2019-08-16 | 2019-12-31 | 西安航天三沃化学有限公司 | Flame-retardant acrylate pressure-sensitive adhesive as well as preparation method and application thereof |
| CN110655618A (en) * | 2019-09-06 | 2020-01-07 | 广东弘擎电子材料科技有限公司 | Strong acid and strong base resistant and flame retardant pressure-sensitive adhesive and preparation method thereof |
| CN110684491A (en) * | 2019-10-31 | 2020-01-14 | 深圳市益达兴科技股份有限公司 | High-viscosity flame-retardant environment-friendly pressure-sensitive adhesive, preparation method thereof and preparation method of pressure-sensitive adhesive film |
| CN111040684A (en) * | 2019-12-28 | 2020-04-21 | 太仓运通新材料科技有限公司 | Preparation method of flame-retardant modified acrylate pressure-sensitive adhesive |
| CN113024790A (en) * | 2021-02-04 | 2021-06-25 | 东莞市德聚胶接技术有限公司 | Intrinsic flame-retardant acrylate oligomer and acrylate structural adhesive |
| CN113512384A (en) * | 2021-06-10 | 2021-10-19 | 江阴邦特科技有限公司 | Water-based acrylic flame-retardant adhesive and preparation method thereof |
| CN114854209A (en) * | 2016-11-30 | 2022-08-05 | 兰达实验室（2012）有限公司 | Process for preparing a composition comprising carbon black |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1833012A (en) * | 2003-08-08 | 2006-09-13 | 3M创新有限公司 | Halogen-free flame-retardant acrylic pressure-sensitive adhesive sheet or tape |
| CN1916098A (en) * | 2005-08-15 | 2007-02-21 | 上海化工研究院 | Flame resisting agent with no halogen in series of crylic acid in use for pressure sensitive adhesive tape, and prepartion method |
| JP2007297640A (en) * | 1995-11-27 | 2007-11-15 | 3M Co | Pressure-sensitive adhesive composition and tapes |
| CN101781535A (en) * | 2010-02-25 | 2010-07-21 | 北京高盟化工有限公司 | Solvent based flame-retardant pressure-sensitive binding agent and preparation method thereof |
| CN201904043U (en) * | 2010-03-20 | 2011-07-20 | 厦门市英诺尔电子科技有限公司 | Anti-static label material |
| CN102220093A (en) * | 2011-05-30 | 2011-10-19 | 苏州市安特菲尔新材料有限公司 | Composite flame-retardant film and preparation method thereof |
-
2011
- 2011-12-27 CN CN201110444349.0A patent/CN102518003B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297640A (en) * | 1995-11-27 | 2007-11-15 | 3M Co | Pressure-sensitive adhesive composition and tapes |
| CN1833012A (en) * | 2003-08-08 | 2006-09-13 | 3M创新有限公司 | Halogen-free flame-retardant acrylic pressure-sensitive adhesive sheet or tape |
| CN1916098A (en) * | 2005-08-15 | 2007-02-21 | 上海化工研究院 | Flame resisting agent with no halogen in series of crylic acid in use for pressure sensitive adhesive tape, and prepartion method |
| CN101781535A (en) * | 2010-02-25 | 2010-07-21 | 北京高盟化工有限公司 | Solvent based flame-retardant pressure-sensitive binding agent and preparation method thereof |
| CN201904043U (en) * | 2010-03-20 | 2011-07-20 | 厦门市英诺尔电子科技有限公司 | Anti-static label material |
| CN102220093A (en) * | 2011-05-30 | 2011-10-19 | 苏州市安特菲尔新材料有限公司 | Composite flame-retardant film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 贺贤璋 等: "国内特种纸用造纸化学品的应用现状和发展趋向", 《杭州化工》 * |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103568456A (en) * | 2012-07-24 | 2014-02-12 | 苏州维艾普新材料有限公司 | Compounding technology by taking polyacrylic acid as adhesive |
| CN102941707A (en) * | 2012-11-01 | 2013-02-27 | 广州市金万正印刷材料有限公司 | Soft laser self-adhesive label film and preparation method thereof |
| CN104099044A (en) * | 2013-04-02 | 2014-10-15 | 联冠(开平)胶粘制品有限公司 | Label adhesive for sticking on oil stain surface and preparation method thereof |
| CN103834329A (en) * | 2014-03-18 | 2014-06-04 | 苏州斯迪克新材料科技股份有限公司 | Halogen-free environment-friendly adhesive and preparation method thereof |
| CN103834329B (en) * | 2014-03-18 | 2016-01-20 | 苏州斯迪克新材料科技股份有限公司 | A kind of halogen-free environmental sizing agent and preparation method thereof |
| WO2017153227A1 (en) * | 2016-03-10 | 2017-09-14 | Clariant Plastics & Coatings Ltd | Halogen-free, intumescent fire-proof coating, and use thereof |
| CN105702155B (en) * | 2016-04-13 | 2019-04-26 | 广盟（广州）包装有限公司 | A kind of compound label and its production technology |
| CN105702155A (en) * | 2016-04-13 | 2016-06-22 | 广盟（广州）包装有限公司 | Composite label and production process thereof |
| CN106398596A (en) * | 2016-08-31 | 2017-02-15 | 潍坊恒彩数码影像材料有限公司 | Flame-retardant glue |
| CN114854209B (en) * | 2016-11-30 | 2023-08-18 | 兰达实验室（2012）有限公司 | Method for preparing a composition comprising carbon black |
| CN114854209A (en) * | 2016-11-30 | 2022-08-05 | 兰达实验室（2012）有限公司 | Process for preparing a composition comprising carbon black |
| CN108285546A (en) * | 2018-03-01 | 2018-07-17 | 苏州维洛克电子科技有限公司 | A kind of fire retardant mylar and preparation method thereof of without phosphorus Halogen |
| CN108510874A (en) * | 2018-04-08 | 2018-09-07 | 深圳昌茂粘胶新材料有限公司 | Fire-retardant label of a kind of self-bleeding battery of environmental protection and preparation method thereof |
| CN108864976A (en) * | 2018-08-10 | 2018-11-23 | 阜南县力韦包装材料有限公司 | A kind of fire-retardant mightiness belt of waterproof antiwear |
| CN109294490A (en) * | 2018-10-14 | 2019-02-01 | 佛山市顺德区永创翔亿电子材料有限公司 | Battery flame-retardant adhesive and preparation method and battery single layer fire retardant insulating indigo plant film |
| CN109294490B (en) * | 2018-10-14 | 2020-11-13 | 佛山市顺德区永创翔亿电子材料有限公司 | Battery flame-retardant adhesive, preparation method thereof and single-layer flame-retardant insulating blue film for battery |
| CN109852322A (en) * | 2018-12-04 | 2019-06-07 | 顺德职业技术学院 | Thermally conductive reaction-type flame-retarding polyurethane hot melt of one-component and preparation method thereof |
| CN109797603A (en) * | 2019-01-29 | 2019-05-24 | 上海万戈工贸发展有限公司 | One kind having waterproof low-smoke non-halogen flame-retardant paper and preparation method thereof |
| CN109935159A (en) * | 2019-03-28 | 2019-06-25 | 深圳昌茂粘胶新材料有限公司 | A kind of reticulate pattern heat-conducting glue label material and preparation method thereof with flame retarding function |
| CN109935159B (en) * | 2019-03-28 | 2024-01-26 | 深圳昌茂粘胶新材料有限公司 | Reticulate pattern heat-conducting adhesive label material with flame retardant function and preparation method thereof |
| CN110144096A (en) * | 2019-06-03 | 2019-08-20 | 陕西科技大学 | A kind of flame-retardant polypropelene acid esters lotion and preparation method thereof |
| CN110144096B (en) * | 2019-06-03 | 2021-03-02 | 陕西科技大学 | Flame-retardant polyacrylate emulsion and preparation method thereof |
| CN110407979A (en) * | 2019-08-09 | 2019-11-05 | 苏州高泰电子技术股份有限公司 | Pressure-sensitive gum resin and light transmission flame-retardant double sided tape comprising it |
| CN110628362A (en) * | 2019-08-16 | 2019-12-31 | 西安航天三沃化学有限公司 | Flame-retardant acrylate pressure-sensitive adhesive as well as preparation method and application thereof |
| CN110655618A (en) * | 2019-09-06 | 2020-01-07 | 广东弘擎电子材料科技有限公司 | Strong acid and strong base resistant and flame retardant pressure-sensitive adhesive and preparation method thereof |
| CN110684491A (en) * | 2019-10-31 | 2020-01-14 | 深圳市益达兴科技股份有限公司 | High-viscosity flame-retardant environment-friendly pressure-sensitive adhesive, preparation method thereof and preparation method of pressure-sensitive adhesive film |
| CN111040684A (en) * | 2019-12-28 | 2020-04-21 | 太仓运通新材料科技有限公司 | Preparation method of flame-retardant modified acrylate pressure-sensitive adhesive |
| CN113024790A (en) * | 2021-02-04 | 2021-06-25 | 东莞市德聚胶接技术有限公司 | Intrinsic flame-retardant acrylate oligomer and acrylate structural adhesive |
| CN113512384A (en) * | 2021-06-10 | 2021-10-19 | 江阴邦特科技有限公司 | Water-based acrylic flame-retardant adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102518003B (en) | 2014-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102518003B (en) | Preparation method for halogen-free flame retardant polyester labeled paper | |
| CN102533177B (en) | High water resistance emulsion polyacrylate pressure-sensitive adhesive and preparation method and application thereof | |
| CN101548204B (en) | Pressure-sensitive adhesive for optical films | |
| CN103725231B (en) | Adhesive material for adhesive tapes and preparation method thereof | |
| CN101376796B (en) | Aqueous bottom glue for soft polychloroethylene contact adhesive tape and manufacturing method thereof | |
| WO2007029783A1 (en) | Acrylic adhesive composition and adhesive product | |
| CN103805106A (en) | Water dispersive adhesive composition, preparation method of re-stripping adhesive sheet, and re-stripping adhesive sheet | |
| CN108795307A (en) | A kind of very thin double faced adhesive tape and preparation method thereof | |
| CN107779096B (en) | A kind of production method of the uncured rubber asphalt waterproof coating of novel low cigarette environmental protection | |
| CN104354362A (en) | Ultrahigh-barrier transparent aluminum oxide plated thin film and manufacturing method thereof | |
| CN103773260A (en) | Preparation method of optical transparent two-sided sticky tape | |
| CN103834320A (en) | Re-peel-off type special double-faced adhesive sheet for fixing flexible printed circuit board | |
| CN103122048B (en) | Thermoplastic acrylic resin | |
| TW202000831A (en) | Flame-retardant pressure-sensitive adhesive, flame-retardant pressure-sensitive adhesive sheet and method for preparing same | |
| CN111154429B (en) | Polyacrylate pressure-sensitive adhesive | |
| KR102035040B1 (en) | Easily dismantled adhesive agent composition and easily dismantled adhesive tape | |
| CN110628362A (en) | Flame-retardant acrylate pressure-sensitive adhesive as well as preparation method and application thereof | |
| CN109401692A (en) | A kind of silk-screen printing glue and preparation method thereof | |
| CN103275657B (en) | Peelable release flame-proof acrylic ester pressure-sensitive | |
| CN103608420B (en) | Easy decomposability binder composition and easily decomposability self adhesive tape | |
| CN103361011B (en) | A kind of adhesive compound and a kind of joint sealing sealing tape | |
| CN105254866A (en) | Carboxyl-terminated phosphorus-containing copolyester, preparation method, halogen-free flame retardant biology-based pressure sensitive adhesive composed of carboxyl-terminated phosphorus-containing copolyester and application | |
| CN102220093A (en) | Composite flame-retardant film and preparation method thereof | |
| CN111825830B (en) | Modified phytic acid derivative resin, light-curable liquid flame-retardant resin and flame-retardant film and preparation method thereof | |
| CN103275658B (en) | The preparation method of peelable release flame-proof acrylic ester pressure-sensitive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: Samsung road 621000 Mianyang city of Sichuan province Youxian District No. 188 Applicant after: Sichuan Dongcai Technology Group Co., Ltd. Address before: 621000 Mianyang City, Sichuan province Youxian District No. 6 Dongxing Road Applicant before: Sichuan Dongcai Technology Group Co., Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |