CN108148533A - A kind of hot melt adhesive for being used for the outer transfer technique of film and preparation method thereof - Google Patents
A kind of hot melt adhesive for being used for the outer transfer technique of film and preparation method thereof Download PDFInfo
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- CN108148533A CN108148533A CN201810063461.1A CN201810063461A CN108148533A CN 108148533 A CN108148533 A CN 108148533A CN 201810063461 A CN201810063461 A CN 201810063461A CN 108148533 A CN108148533 A CN 108148533A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The present invention relates to a kind of hot melt adhesive for transfer technique outside film, include the substance of following mass fraction：Basic resin 30 ~ 40%；Tackifier 10 ~ 15%；Viscosity-controlling agent 5 ~ 10%；Antioxidant 5 ~ 10%；Organic solvent 25 ~ 50%；Wherein, the basic resin is synthesized by being modified vinyl chloride-vinyl acetate resin and saturated polyester under the action of diisocyanate.Hot melt adhesive in the present invention is thermoplastic, does not need to addition curing agent, end product properties are stable, reservoir is long；Peel strength is high, suitable for the film that the flexibility of OMD techniques is smooth；Preparation method is simple and practicable, suitable for large-scale production.
Description
Technical field
The present invention relates to hot melt adhesive field more particularly to a kind of hot melt adhesive and its preparation side for the outer transfer technique of film
Method.
Background technology
OMD (Out-side Model Decoration) mould external decoration technology is that pattern and character is printed in transparent membrane
Afterwards, picture and text are directly coated on by plastics using high pressure vacuum transfer or metal surface forms a kind of incrustation skill of three-dimensional application
Art, transparent membrane therein are the carriers of picture and text.First at 150 DEG C or so by thermal softening when OMD transfer films transfer pattern, then
10~15s of body surface or so is tightly adsorbed onto under the decompression of vacuum pump, base material of tearing after the completion of fitting, pattern is left in
Body surface.
OMD transfer films are the cores of the outer transfer technique of mould, and different function layer has the function of different on transfer film, wherein glue
Layer provides pattern layer and the binding force of body surface, and the performance of hot melt adhesive used in glue-line determines whether pattern layer persistently endures hardships,
Whether can reach requirement by decorating objects.There are related patents to disclose and be related to adhesive used in thermal transfer, such as patent
Number it is：The patent of CN201210436409.9 disclose it is a kind of using epoxy resin for main component prepare for glass base
Thermal transfer adhesive；The patent of patent No. CN201210436137.2 discloses a kind of using polyurethane and acrylate as curing
Thermal transfer adhesive, heat transfer film and heat-transferring method prepared by system；Patent No. CN201310194469.9 discloses one
Kind epoxy resin and polyurethane compound thermal transfer glue and preparation method thereof；The patent of Patent No. CN201310194492.8 is public
A kind of Acrylic resin thermal transfer glue and preparation method thereof is opened.More than patent is directed to the adhesive used in thermal transfer, but its
In all used curing agent, belong to Thermosetting adhesive.Such adhesive when in use adds in curing agent in adhesive so
After prepare transfer film, can cause in this way transfer film properties it is unstable, Storage period is short, bad adaptability.Under the higher environment of room temperature,
Curing agent increased activity is easy to cause adhesive premature cure, transfer film is enabled to scrap.In addition, Patent No.
The patent of CN200910099377.6 discloses a kind of polyurethane hot melt adhesive for high-grade lining cloth and preparation method thereof；Patent No.
The patent of CN201310277072.6 discloses a kind of preparation method of special composite hot melt adhesive for polyvinyl chloride decorative board；
The patent of CN201510497729.9 discloses a kind of modified poly ester hot melt adhesive and its preparation method of glued membrane.Patent No.
The patent of CN201710451041.6 discloses a kind of polyester amide hot melt adhesive and preparation method thereof.OMD has specific technique to join
Number, transfer temperature are 120~150 DEG C, and curing temperature is 60~100 DEG C, and 20~40s of transfer time, transfer pressure is air source
Pressure 8Kg/m2, more than patent belong to Thermoplastic hot melt glue, but application scenario is different, the Thermodynamic Criteria of involved hot melt adhesive
It is not consistent with OMD techniques.Moreover, the material that OMD techniques are decorated is diversified, it is poly- involved by above-mentioned partial monopoly
Ester hot melt adhesive is only applicable to the shaggy product such as cloth, timber, and surface adhesive strength that can be low for surface is inadequate.Cause
This, it is also necessary to research and develop a kind of hot melt adhesive suitable for OMD techniques.
Invention content
It is Thermoplastic adhesive it is an object of the invention to propose a kind of hot melt adhesive for transfer technique outside film,
It is applied widely, peel strength is high, suitable for OMD techniques；Preparation is simple for it, suitable for large-scale production.
A kind of hot melt adhesive for the outer transfer technique of film includes the substance of following mass fraction：
Wherein, the basic resin is synthesized by being modified vinyl chloride-vinyl acetate resin and saturated polyester under the action of diisocyanate.
In some embodiments, the substance for synthesizing the basic resin is diisocyanate, is modified vinyl chloride-vinyl acetate resin and saturation
Polyester, the mass fraction ratio of three is 1~2: 2~3: 5~7.
In some embodiments, the modified vinyl chloride-vinyl acetate resin is by N-2- amino-ethyl -2- hydroxypropanamides and ternary chlorine vinegar
Obtained by resin reaction；
N-2- amino-ethyls -2- the hydroxypropanamides by following mass fraction than material composition,
Lactic acid 45~50%；
Ethylenediamine 50~55%.
In some embodiments, the diisocyanate is toluene di-isocyanate(TDI), isophorone diisocyanate, hexichol
In dicyclohexylmethane diisocyanate, dicyclohexyl methyl hydride diisocyanate, hexamethylene diisocyanate, lysine diisocyanate
It is one or more.
In some embodiments, the ternary chlorine vinegar resin is that the ternary of vinylacetate, vinyl chloride and maleic anhydride is gathered
Close object；The mass fraction of three is
Vinylacetate 13~15%；
Vinyl chloride 81~84%
Maleic anhydride 1~6%.
In some embodiments,：The saturated polyester is the high score that dihydric alcohol and binary acid are obtained through dehydration condensation
Sub- polymer, the molecular weight of the saturated polyester is 10000~50000；The dihydric alcohol is ethylene glycol, propylene glycol and butanediol
In it is one or more；The binary acid is one or more in terephthalic acid (TPA), M-phthalic acid and phthalic acid.
The invention also discloses a kind of method for preparing above-mentioned hot melt adhesive, including：
Step (1), by basic resin and organic solvent merging in the container with agitating device, control temperature 30~
35 DEG C, stirring and dissolving；
Step (2) sequentially adds tackifier, viscosity-controlling agent and antioxidant, is warming up to 60~80 DEG C, and sealing container is stirred
It mixes 30~40 minutes；
Step (3) stops heating, keeps the temperature 30 minutes, makes its cooled to room temperature.
In some embodiments, the preparation method of the basic resin includes：
Step A, saturated polyester is dissolved in organic solvent, wherein the mass fraction of saturated polyester is 40~50%, organic
The mass fraction of solvent is 50~60%；
Step B, modified vinyl chloride-vinyl acetate resin and diisocyanate are added in, it is 60~80 DEG C that reaction temperature is kept in four-hole bottle,
React 2h.
In some embodiments, the preparation method of the modified vinyl chloride-vinyl acetate resin includes：
Step a, it weighs appropriate lactic acid and ethylenediamine is placed in reaction vessel, slow reaction 30 divides in the environment of -5 DEG C
Reactant when reactant is converted into pale yellow oily liquid, is placed in drying in 60 DEG C of baking oven, obtains N-2- amino second by clock
Base -2- hydroxypropanamides；
Step b, ternary chlorine vinegar resin is dissolved in organic solvent, wherein the mass fraction of ternary chlorine vinegar resin for 20~
30%, the mass fraction of organic solvent is 70~80%；
Step c, the N-2- ammonia for being equivalent to 5%~8% mass fraction of ternary chlorine vinegar resin is added in the solution of step b
Base ethyl -2- hydroxypropanamides add in catalytic amount, and 1h is reacted in four-hole bottle, and 105~120 DEG C of reaction temperature takes out reaction
Object is dry in baking oven, and it is spare to remove organic solvent.
In some embodiments, the catalyst is 1~3% sodium hypophosphite.
Advantage is：1st, this hot melt adhesive is thermoplastic, does not need to addition curing agent, end product properties are stable, storage
Storage is long；2nd, peel strength is high, suitable for the film that the flexibility of OMD techniques is smooth；3rd, preparation method is simple and practicable, suitable for big
Large-scale production.
Description of the drawings
Fig. 1 is the process of synthesis modification agent N-2- amino-ethyl -2- hydroxypropanamides (NHPA) in the present invention.
Fig. 2 is the schematic diagram that basic resin is synthesized in the present invention.
Fig. 3 is the structure that the strand of modified vinyl chloride-vinyl acetate resin and the strand of saturated polyester are grafted by diisocyanate
Figure.
Fig. 4 is hot melt adhesive strength of glass test result.
Wherein, a represents that ethylenediamine and production of lactic acid EHPA, b represent that EHPA reacts production by-product, V0 representatives pair with lactic acid
Ratio 0, V1 represent embodiment 1, and V2 represents embodiment 2, and V3 represents embodiment 3, and V4 represents embodiment 4.
Specific embodiment
Illustrate technical scheme of the present invention below in conjunction with the accompanying drawings.
A kind of hot melt adhesive for the outer transfer technique of film includes the substance of following mass fraction：
Wherein, the basic resin is synthesized by being modified vinyl chloride-vinyl acetate resin and saturated polyester under the action of diisocyanate.
The tackifier are rosin, modified rosin, C5 Petropols, C9 Petropols, one kind in terpene resin or several
Kind, for increasing adhesive strength.
The viscosity modifier is one or more of paraffin, microwax, synthetic wax (PE or PP), Buddhist support wax.
The antioxidant is pentaerythritol ester, the positive octadecanol ester of the propionic acid, (2- methyl -4- hydroxyl -5- uncles of 1,1,3- tri-
Butylbenzene base) butane, three (nonyl phenyl) phosphite esters etc..
The organic solvent is butanone, cyclohexanone, acetone, toluene, dimethylbenzene, ethyl acetate, butyl acetate, acetic acid isopropyl
Ester it is one or more.
In some embodiments, the substance for synthesizing the basic resin is diisocyanate, is modified vinyl chloride-vinyl acetate resin and saturation
Polyester, the mass fraction ratio of three is 1~2: 2~3: 5~7.
There are a large amount of ester bonds in the main chain of saturated polyester, ester bond is easily hydrolyzed under acid or alkali environment and ultraviolet light, is broken, causes
Polyester hot-melt adhesive resistance to acid and alkali is poor, has the interpenetrating networks knot formed by vinyl chloride-vinyl acetate resin and saturated polyester by modified polyester
Structure, vinyl chloride-vinyl acetate resin have good resistance to acid and alkali, and molecular weight has the function of ester bond winding package, and protection effect is played to it
Fruit, therefore improve the acid and alkali-resistance and weatherability of manufactured hot melt adhesive.
In some embodiments, the modified vinyl chloride-vinyl acetate resin is by N-2- amino-ethyl -2- hydroxypropanamides and ternary chlorine vinegar
Obtained by resin reaction；
N-2- amino-ethyls -2- the hydroxypropanamides by following mass fraction than material composition,
Lactic acid 45~50%；
Ethylenediamine 50~55%.
It is prepared as shown in Figure 1, carrying out amidation process using carboxyl in primary amine groups in ethylenediamine and lactic acid with amido
The modifying agent N-2- amino-ethyl -2- hydroxypropanamides (NHPA) of two different functional groups of (- NH2) and hydroxyl (- OH).Meanwhile
There is carboxyl (- COOH) on the main chain of ternary chlorine vinegar resin, using the high characteristic of amidated reactivity ratio's esterification,
Make modifying agent NHPA and ternary chlorine vinegar resin reaction under certain condition, its-COOH is converted into-OH.In ethylenediamine and lactic acid
In chemical reaction, there are two reaction routes, wherein a refers to that ethylenediamine and production of lactic acid EHPA, b refer to that EHPA reacts again with lactic acid
By-product is produced, if by-product is excessive, EHPA is just few, vinyl chloride-vinyl acetate resin can be caused to be modified insufficient.It is preferred, therefore, that synthesis
During NHPA, the mass fraction of ethylenediamine is more than the mass fraction of lactic acid, helps to react the direction progress to generation NHPA.
In some embodiments, the diisocyanate is toluene di-isocyanate(TDI), isophorone diisocyanate, hexichol
In dicyclohexylmethane diisocyanate, dicyclohexyl methyl hydride diisocyanate, hexamethylene diisocyanate, lysine diisocyanate
It is one or more.
As shown in Figures 2 and 3, modified vinyl chloride-vinyl acetate resin and saturated polyester can be sent out all with hydroxyl (- OH) with diisocyanate
Raw reaction makes the strand of vinyl chloride-vinyl acetate resin and the strand of saturated polyester by together with diisocyanate grafting.This method
Multi-functional vinyl chloride-vinyl acetate resin is grafted on saturated polyester strand, saturated polyester is made to contain more functional groups, is improved
Hot melt adhesive is to the adaptability of adhesives.
In some embodiments, the ternary chlorine vinegar resin is that the ternary of vinylacetate, vinyl chloride and maleic anhydride is gathered
Close object；The mass fraction of three is
Vinylacetate 13~15%；
Vinyl chloride 81~84%
Maleic anhydride 1~6%.
Vinyl chloride-vinyl acetate resin has superior adherence to metal especially aluminium, to PVC product, paper, fiber, glass, ceramic tile, sand
Stone, timber also have excellent adherence.
In some embodiments, the saturated polyester is the macromolecule that dihydric alcohol and binary acid are obtained through dehydration condensation
Polymer, the molecular weight of the saturated polyester is 10000~50000；The dihydric alcohol is in ethylene glycol, propylene glycol and butanediol
It is one or more；The binary acid is one or more in terephthalic acid (TPA), M-phthalic acid and phthalic acid.
With phenyl ring in the binary acid of synthesizing polyester, molcohesion can be provided.
The invention also discloses a kind of method for preparing hot melt adhesive as described above, including：
Step (1), by basic resin and organic solvent merging in the container with agitating device, control temperature 30~
35 DEG C, stirring and dissolving；
Step (2) sequentially adds tackifier, viscosity-controlling agent and antioxidant, is warming up to 60~80 DEG C, and sealing container is stirred
It mixes 30~40 minutes；
Step (3) stops heating, keeps the temperature 30 minutes, makes its cooled to room temperature.
In some embodiments, the preparation method of the basic resin includes：
Step A, saturated polyester is dissolved in organic solvent, wherein the mass fraction of saturated polyester is 40~50%, organic
The mass fraction of solvent is 50~60%；
Step B, modified vinyl chloride-vinyl acetate resin and diisocyanate are added in, it is 60~80 DEG C that reaction temperature is kept in four-hole bottle,
React 2h.
Condensing unit and agitating device are also carried in four-hole boiling flask.
In some embodiments, the preparation method of the modified vinyl chloride-vinyl acetate resin includes：
Step a, it weighs appropriate lactic acid and ethylenediamine is placed in reaction vessel, slow reaction 30 divides in the environment of -5 DEG C
Reactant when reactant is converted into pale yellow oily liquid, is placed in drying in 60 DEG C of baking oven, obtains N-2- amino second by clock
Base -2- hydroxypropanamides；
Step b, ternary chlorine vinegar resin is dissolved in organic solvent, wherein the mass fraction of ternary chlorine vinegar resin for 20~
30%, the mass fraction of organic solvent is 70~80%；
Step c, the N-2- ammonia for being equivalent to 5%~8% mass fraction of ternary chlorine vinegar resin is added in the solution of step b
Base ethyl -2- hydroxypropanamides add in catalytic amount, and 1h is reacted in four-hole bottle, and 105~120 DEG C of reaction temperature takes out reaction
Object is dry in baking oven, and it is spare to remove organic solvent.
In step a, since the reaction of ethylenediamine and lactic acid is very active, side reaction can occur under room temperature, therefore reduce anti-
Temperature is answered to be conducive to that reaction is made to move to target product.In step c, four-hole boiling flask carries distilling apparatus and agitating device；
Drying is to remove unreacted ethylenediamine impurity in baking oven.
In some embodiments,：The catalyst is 1~3% sodium hypophosphite.
Sodium hypochlorite is amidation catalyst, and the reaction is amidation process.
The technical solution that by the following specific examples further illustrate the invention.
Embodiment 1
First, basic resin is prepared in accordance with the following steps：
Step 1, according to mass fraction than lactic acid 50%, ethylenediamine 50% weighs reactant and is placed in reaction vessel ,-
Slow reaction 30 minutes in 5 DEG C of refrigerator, when reactant is converted into pale yellow oily liquid, by reactant as 60 DEG C of baking
It is dry in case, unreacted ethylenediamine is removed, obtains N-2- amino-ethyl -2- hydroxypropanamides (NHPA).
Step 2, with mass fraction than butanone: toluene=1: 1 ratio prepares organic solvent, by ternary chlorine vinegar resin (by
Mass fraction is synthesized by 13% vinylacetate, 81% vinyl chloride and 6% maleic anhydride) it is dissolved in organic solvent
In prepare solution, wherein ternary chlorine vinegar resin 20%, solvent 80%,
Step 3 adds in the NHPA for being equivalent to 5% mass fraction of ternary chlorine vinegar resin in the solution of step 2, adds in 1%
The sodium hypophosphite of catalytic amount, reacts 1h in the four-hole bottle with distilling apparatus and agitating device, and 105 DEG C of reaction temperature is taken out
For reactant with dry in baking oven, removing solvent is spare.
Saturated polyester is dissolved in matched organic solvent and prepares solution by step 4, wherein saturated polyester 40%, organic solvent
It is 60%.
Step 5 adds in above-mentioned modified vinyl chloride-vinyl acetate resin and diisocyanate, and mass fraction ratio is diisocyanate: modified
Vinyl chloride-vinyl acetate resin: saturated polyester=1: 3: 6, controlling reaction temperature is 80 DEG C, in the four-hole bottle with condensing unit and agitating device
Middle reaction 2h obtains the copolymer of saturated polyester and vinyl chloride-vinyl acetate resin.
2nd, hot melt adhesive is prepared according to formula as below：
Preparation process is as follows：
Step (1) in the container with agitating device, controls basic resin and organic solvent merging according to above-mentioned formula
Temperature processed is at 35 DEG C, stirring and dissolving.
Step (2) sequentially adds rosin, modified rosin, paraffin, pentaerythritol ester, is warming up to 80 DEG C, and sealing container is stirred
It mixes 30 minutes.
Step (3) terminates heating unit, keeps the temperature 30 minutes, makes its cooled to room temperature.
Embodiment 2
First, basic resin is prepared in accordance with the following steps：
Step 1, according to mass fraction than lactic acid 45%, ethylenediamine 55% weighs reactant and is placed in reaction vessel ,-
Slow reaction 30 minutes in 5 DEG C of refrigerator, when reactant is converted into pale yellow oily liquid, by reactant as 60 DEG C of baking
It is dry in case, unreacted ethylenediamine is removed, obtains N-2- amino-ethyl -2- hydroxypropanamides (NHPA).
Step 2, with mass fraction than cyclohexanone: acetone=1: 1 prepare solvent, by ternary chlorine vinegar resin (by mass fraction
Synthesized by 15% vinylacetate, 84% vinyl chloride and 1% maleic anhydride) it is dissolved in preparing solution in solvent,
Middle ternary chlorine vinegar resin 30%, solvent 70%,
Step 3 adds in the NHPA for being equivalent to 8% mass fraction of ternary chlorine vinegar resin in the solution of step 2, adds in 2%
The sodium hypophosphite of catalytic amount reacts 1h in the four-hole bottle with distilling apparatus and agitating device, and it is 105 to keep reaction temperature
DEG C, reactant is taken out with dry in baking oven, and removing solvent is spare.
Saturated polyester is dissolved in matched solvent and prepares solution by step 4, and wherein saturated polyester 40%, organic solvent are
60%.
Step 5 adds in above-mentioned modified vinyl chloride-vinyl acetate resin and diisocyanate, and mass fraction ratio is diisocyanate: modified
Vinyl chloride-vinyl acetate resin: saturated polyester=2: 3: 5, controlling reaction temperature is 60 DEG C, in the four-hole bottle with condensing unit and agitating device
Middle reaction 2h obtains the copolymer of saturated polyester and vinyl chloride-vinyl acetate resin.
2nd, hot melt adhesive is prepared according to formula as below：
Preparation process is as follows：
Basic resin and solvent merging in the container with agitating device, are controlled temperature by step (1) according to above-mentioned formula
Degree is at 30 DEG C, stirring and dissolving.
Step (2) sequentially adds the positive octadecanol ester of C5 Petropols, microwax, propionic acid, is warming up to 60 DEG C, sealing
Container stirs 40 minutes.
Step (3) terminates heating unit, keeps the temperature 30 minutes, makes its cooled to room temperature.
Embodiment 3
First, basic resin is prepared in accordance with the following steps：
Step 1, according to mass fraction than lactic acid 45%, ethylenediamine 55% weighs reactant and is placed in reaction vessel ,-
Slow reaction 30 minutes in 5 DEG C of refrigerator, when reactant is converted into pale yellow oily liquid, by reactant as 60 DEG C of baking
It is dry in case, unreacted ethylenediamine is removed, obtains N-2- amino-ethyl -2- hydroxypropanamides (NHPA).
Step 2, with quality than dimethylbenzene, ethyl acetate=1: 1.5 prepare solvents, by ternary chlorine vinegar resin (by quality point
Number for 14% vinylacetate, 83% vinyl chloride and 3% maleic anhydride synthesis) be dissolved in match solvent in prepare solution,
Wherein ternary chlorine vinegar resin 20%, solvent 80%,
Step 3 adds in the NHPA for being equivalent to 5% mass fraction of ternary chlorine vinegar resin in the solution of step 2, adds in 3%
The sodium hypophosphite of catalytic amount, reacts 1h in the four-hole bottle with distilling apparatus and agitating device, and 120 DEG C of reaction temperature is taken out
For reactant with dry in baking oven, removing solvent is spare.
Saturated polyester is dissolved in matched solvent and prepares solution by step 4, and wherein saturated polyester 50%, organic solvent are
50%.
Step 5 adds in above-mentioned modified ternary chlorine vinegar resin and diisocyanate, and mass ratio is diisocyanate: modified
Vinyl chloride-vinyl acetate resin: saturated polyester=1: 2: 7, controlling reaction temperature is 80 DEG C, in the four-hole bottle with condensing unit and agitating device
Middle reaction 2h obtains the copolymer of saturated polyester and vinyl chloride-vinyl acetate resin.
2nd, hot melt adhesive is prepared according to formula as below：
Preparation process is as follows：
Basic resin and solvent merging in the container with agitating device, are controlled temperature by step (1) according to above-mentioned formula
Degree is at 35 DEG C, stirring and dissolving.
Step (2) sequentially adds C9 oil tree, synthetic wax, 1,1,3- tri- (2- methyl -4- hydroxyl -5- 2-methyl-2-phenylpropanes base) fourth
Alkane, is warming up to 60 DEG C, and sealing container stirs 40 minutes.
Step (3) terminates heating unit, keeps the temperature 30 minutes, makes its cooled to room temperature.
Embodiment 4
First, basic resin is prepared in accordance with the following steps：
Step 1, according to mass fraction than lactic acid 50%, ethylenediamine 50% weighs reactant and is placed in reaction vessel ,-
Slow reaction 30 minutes in 5 DEG C of refrigerator, when reactant is converted into pale yellow oily liquid, by reactant as 60 DEG C of baking
It is dry in case, unreacted ethylenediamine is removed, obtains N-2- amino-ethyl -2- hydroxypropanamides (NHPA).
Step 2, with quality than butyl acetate, isopropyl acetate=1: 2 prepare solvents, by ternary chlorine vinegar resin (by quality
Score is synthesized by 14% vinylacetate, 82% vinyl chloride and 4% maleic anhydride) be dissolved in it is molten with preparing in solvent
Liquid, wherein ternary chlorine vinegar resin 25%, solvent 75%.
Step 3 adds in the NHPA for being equivalent to 5% mass fraction of ternary chlorine vinegar resin in the solution of step 2, adds in 2%
The sodium hypophosphite of catalytic amount, reacts 1h in the four-hole bottle with distilling apparatus and agitating device, and 115 DEG C of reaction temperature is taken out
For reactant with dry in baking oven, removing solvent is spare.
Saturated polyester is dissolved in matched solvent and prepares solution by step 4, and wherein saturated polyester 45%, organic solvent are
55%.
Step 5 adds in above-mentioned modified vinyl chloride-vinyl acetate resin and diisocyanate, and mass ratio is diisocyanate: modified chlorine vinegar
Portions of resin saturated polyester=1: 3: 6, controlling reaction temperature is 80 DEG C, anti-in the four-hole bottle with condensing unit and agitating device
2h is answered to obtain the copolymer of saturated polyester and vinyl chloride-vinyl acetate resin.
2nd, hot melt adhesive is prepared according to formula as below：
Preparation process is as follows：
Basic resin and solvent merging in the container with agitating device, are controlled temperature by step (1) according to above-mentioned formula
Degree is at 30 DEG C, stirring and dissolving.
Step (2) sequentially adds terpene resin, Buddhist support wax, three (nonyl phenyl) phosphite esters, is warming up to 60 DEG C, sealing
Container stirs 30 minutes.
Step (3) terminates heating unit, keeps the temperature 30 minutes, makes its cooled to room temperature.
Performance test experimental data
1st, hot melt adhesive thermodynamic property is tested
Test method：Hot melt adhesive is characterized using DSC and TG, as a result such as table 1.
1 hot melt adhesive thermodynamic property test result of table
| Embodiment | Glass transition temperature (DEG C) | Softening temperature (DEG C) | Decomposition temperature (DEG C) |
| Comparative example 0 | 15.5 | 80.2 | 334.0 |
| Embodiment 1 | 38.3 | 122.6 | 376.3 |
| Embodiment 2 | 40.5 | 125.4 | 384.5 |
| Embodiment 3 | 39.6 | 120.7 | 379.6 |
| Embodiment 4 | 37.2 | 118.7 | 374.2 |
Wherein comparative example 0 is unmodified saturated resin, and from data, the glass transition temperature of unmodified saturated resin is inclined
Low, prepared transfer film properties are unstable, may soften in advance in the higher working environment of temperature, influence technique.From reality
The data for applying example 1~4 can be seen that resin by above-mentioned modification, and glass transition temperature is improved to 37~40 DEG C, improves transfer
Membrane stability, while softening temperature is improved to 118~122 DEG C, this temperature meets the operating temperature transferred outside mould, in addition decomposes
Temperature is promoted to 374~384 DEG C from 334 DEG C, improves the heat resistance of hot melt adhesive.
2nd, peel strength test
Test method：Hot melt adhesive is tested according to 180 ° of peel strength test standard ISO 8510-2-2006, as a result
Such as Fig. 4.
Wherein comparative example 0 is unmodified saturated polyester, is seen by peel strength experimental result, gathered through the above-mentioned saturation being modified
The peel strength of ester is promoted to 2.55~3.03KN/m from 1.56KN/m, and the bonding quality of hot melt adhesive gets a promotion, and improves and turns
Figure layer is attached to by the adhesive force on decorating objects surface in die, optimizes decorative quality.
3rd, hot melt adhesive material adaptive testing
Test method：Melt viscosity is connected on different materials surface, including PET plastic, ABS plastic, PC plastics, glass
Piece, aluminium flake, copper sheet.Then it is tested according to 180 ° of peel strength test standard ISO 8510-2-2006.As a result such as table 3.
3 hot melt adhesive material adaptive testing result of table
| Intensity (KN/m) | PET plastic | ABS plastic | PC plastic | Sheet glass | Aluminium flake | Copper sheet |
| Comparative example | 2.01 | 1.73 | 1.65 | 1.22 | 1.56 | 1.02 |
| Embodiment 1 | 2.68 | 1.89 | 2.74 | 1.76 | 2.55 | 2.28 |
| Embodiment 2 | 2.90 | 2.34 | 2.90 | 1.98 | 3.03 | 2.34 |
| Embodiment 3 | 2.85 | 2.67 | 2.34 | 2.31 | 2.86 | 2.51 |
| Embodiment 4 | 2.79 | 2.56 | 2.12 | 2.24 | 2.73 | 2.45 |
Wherein comparative example 0 is 180 ° of strippings for one of unmodified saturated polyester, requirement of the OMD transfer techniques to hot melt adhesive
Intensity is more than 2.0KN/m, can be seen that unmodified saturated polyester by data in table and only the peel strength of PET is more than
2.0KN/m, and the quantity that the peel strength of 1~4 pair of material of Samples EXAMPLE reaches standard all increased.Such as embodiment 1
Standard is reached to the peel strength of PET, PC, aluminium, copper.Therefore, the adaptability of material increased by modified polyester,
Expand the decoration range of OMD technologies.
4th, the acid and alkali-resistance of hot melt adhesive and weatherability test
Test method：Hot melt adhesive is bonded on aluminium flake and prepares bonding test specimen, bonding test specimen is respectively placed in outdoor, artificial
In sweat, hydrochloric acid solution (0.1mol/L), sodium hydroxide solution (0.1mol/L), surveyed respectively first day, third day, the 7th day
Try its peel strength.Test result is shown in Table 4.
4 hot melt adhesive acid and alkali-resistance of table, that is, weatherability test result
As can be seen from the table, comparative example after tested liquid impregnate after peel strength have greater loss, this is because saturation is gathered
There are a large amount of ester bonds in the main chain of ester, ester bond is easily hydrolyzed under acid or alkali environment and ultraviolet light, is broken, and causes polyester hot-melt adhesive acidproof
The phenomenon that alkaline difference.Polyester through above-mentioned modification shows preferable resistance in test fluid, such as Samples EXAMPLE 1 exists
HCl impregnate one day, three days, seven days after peel strength be respectively 2.43,2.23,1.67KN/m, peel strength has lost
0.76KN/m, and sample comparative example had lost 1.23KN/m after seven days.This is since modified polyester one kind is by vinyl chloride-vinyl acetate resin
The inierpeneirating network structure formed with saturated polyester, vinyl chloride-vinyl acetate resin have good resistance to acid and alkali, and molecular weight has winding to ester bond
The effect of package plays it protective effect, therefore improves its acid and alkali-resistance and weatherability.Hot melt adhesive acid and alkali-resistance and weatherability
Raising, optimize the weatherability of decorative coveringn, extend its service life.
More than content is only presently preferred embodiments of the present invention, for those of ordinary skill in the art, according to the present invention
Thought, there will be changes, the content of the present specification should not be construed as to the present invention in specific embodiments and applications
Limitation, therefore protection scope of the present invention is subject to the range that claim defines.
Claims (10)
1. a kind of hot melt adhesive for the outer transfer technique of film, which is characterized in that include the substance of following mass fraction：
Basic resin 30 ~ 40%；
Tackifier 10 ~ 15%；
Viscosity-controlling agent 5 ~ 10%；
Antioxidant 5 ~ 10%；
Organic solvent 25 ~ 50%；
Wherein, the basic resin is synthesized by being modified vinyl chloride-vinyl acetate resin and saturated polyester under the action of diisocyanate.
2. hot melt adhesive as described in claim 1, which is characterized in that synthesize the substance of the basic resin for diisocyanate,
Modified vinyl chloride-vinyl acetate resin and saturated polyester, the mass fraction ratio of three is 1 ~ 2:2~3:5~7.
3. hot melt adhesive as claimed in claim 2, it is characterised in that：The modified vinyl chloride-vinyl acetate resin is by N-2- amino-ethyl -2- hydroxyls
Obtained by base propionamide and ternary chlorine vinegar resin reaction；
N-2- amino-ethyls -2- the hydroxypropanamides by following mass fraction than material composition,
Lactic acid 45 ~ 50%；
Ethylenediamine 50 ~ 55%.
4. hot melt adhesive as claimed in claim 2, it is characterised in that：The diisocyanate is toluene di-isocyanate(TDI), different Buddhist
That ketone diisocyanate, methyl diphenylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, hexa-methylene diisocyanate
It is one or more in ester, lysine diisocyanate.
5. the basic resin of hot melt adhesive as claimed in claim 3, it is characterised in that：The ternary chlorine vinegar resin is vinyl acetate
The ter-polymers of ester, vinyl chloride and maleic anhydride；The mass fraction of three is
Vinylacetate 13 ~ 15%；
Vinyl chloride 81 ~ 84%
Maleic anhydride 1 ~ 6%.
6. the basic resin of hot melt adhesive as claimed in claim 3, it is characterised in that：The saturated polyester is dihydric alcohol and binary
The high molecular polymer that acid is obtained through dehydration condensation, the molecular weight of the saturated polyester is 10000 ~ 50000；The binary
Alcohol is one or more in ethylene glycol, propylene glycol and butanediol；The binary acid is terephthalic acid (TPA), M-phthalic acid and neighbour
It is one or more in phthalic acid.
7. prepare the method for hot melt adhesive as described in claim 1, which is characterized in that including：
Step（One）, by basic resin and organic solvent merging with agitating device container in, control temperature at 30 ~ 35 DEG C,
Stirring and dissolving；
Step（Two）, sequentially add tackifier, viscosity-controlling agent and antioxidant, be warming up to 60 ~ 80 DEG C, sealing container, stirring 30 ~
40 minutes；
Step（Three）, stop heating, keep the temperature 30 minutes, make its cooled to room temperature.
8. the preparation method of hot melt adhesive as claimed in claim 7, which is characterized in that the preparation method of the basic resin includes：
Step A, saturated polyester is dissolved in organic solvent, wherein the mass fraction of saturated polyester is 40 ~ 50%, organic solvent
Mass fraction is 50 ~ 60%；
Step B, modified vinyl chloride-vinyl acetate resin and diisocyanate are added in, it is 60 ~ 80 DEG C that reaction temperature is kept in four-hole bottle, reacts 2h
.
9. the preparation method of hot melt adhesive as claimed in claim 8, which is characterized in that the preparation method packet of the modified vinyl chloride-vinyl acetate resin
It includes：
Step a, it weighs appropriate lactic acid and ethylenediamine is placed in reaction vessel, slow reaction 30 minutes, are treated in the environment of -5 DEG C
When reactant is converted into pale yellow oily liquid, reactant is placed in drying in 60 DEG C of baking oven, obtains N-2- amino-ethyls -2-
Hydroxypropanamide；
Step b, ternary chlorine vinegar resin is dissolved in organic solvent, wherein the mass fraction of ternary chlorine vinegar resin is 20 ~ 30%, is had
The mass fraction of solvent is 70 ~ 80%；
Step c, the N-2- amino-ethyls -2- for being equivalent to 5% ~ 8% mass fraction of ternary chlorine vinegar resin is added in the solution of step b
Hydroxypropanamide adds in catalytic amount, and 1h is reacted in four-hole bottle, and 105 ~ 120 DEG C of reaction temperature is taken out reactant and done in baking oven
It is dry, it is spare to remove organic solvent.
10. the preparation method of hot melt adhesive as claimed in claim 9, it is characterised in that：The catalyst is 1 ~ 3% sodium hypophosphite.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810063461.1A CN108148533B (en) | 2018-01-23 | 2018-01-23 | Hot melt adhesive for off-film transfer printing technology and preparation method thereof |
| PCT/CN2018/074581 WO2019144420A1 (en) | 2018-01-23 | 2018-01-30 | Hot-melt adhesive used for out-side membrane transfer printing technology and preparation method thereof |
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| CN201810063461.1A CN108148533B (en) | 2018-01-23 | 2018-01-23 | Hot melt adhesive for off-film transfer printing technology and preparation method thereof |
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| CN108148533B CN108148533B (en) | 2021-01-29 |
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Cited By (2)
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| CN110055022A (en) * | 2019-05-13 | 2019-07-26 | 无锡风鹏新材料科技有限公司 | A kind of low melting point, rapid curing, polyester hot-melt adhesive of good fluidity and preparation method thereof |
| CN110143074A (en) * | 2019-05-27 | 2019-08-20 | 青艺（福建）烫画科技有限公司 | Environmental friendly heat transfer printing printed film and preparation method thereof |
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