Specific implementation method is as follows:
A kind of ink powder binding resin composition, by 1 ~ 99 part of linear polyester, 1 ~ 50 part of crosslinked polyester resin, 1 ~ 50 part of modified epoxy composition.
Further, described linear polyester resin Tg is 40 ~ 70 DEG C, and Mn is 1000 ~ 6000, Mw is 8000 ~ 50000, and softening temperature T1/2 is 80 ~ 140 DEG C.Described linear polyester resin is that 100 ~ 200 parts of dibasic acid, 100 ~ 200 parts of dibasic alcohol and 1-3 part catalyzer are occurred esterification condensation reaction removes dereaction generation water after 2 ~ 8 hours at 150 ~ 250 DEG C, then carries out decompression vacuum pumping 0.5 ~ 4 hour to system; Described dibasic acid is terephthalic acid (TPA), m-phthalic acid, phthalic acid, fumaric acid, maleic acid, hexane diacid, decanedioic acid; One in the optional propoxylated bisphenol of dibasic alcohol, Ethoxylated bisphenol A, neopentyl glycol, ethylene glycol, 1,3-PD, BDO or 1,6-hexanediol; Described dibasic alcohol is propoxylated bisphenol, Ethoxylated bisphenol A, ethylene glycol, 1,3-PD.In optimal case, dibasic acid selects terephthalic acid (TPA), fumaric acid, hexanedioic acid; Dibasic alcohol selects the one in propoxylated bisphenol, Ethoxylated bisphenol A or ethylene glycol.Catalyzer can use esterification catalyst well known in the art, as molecular sieve, heteropoly acid, solid super-strong acid, metal-organic complex, organic acid, inorganic salts etc.
Further, described crosslinked polyester resin Tg is 50 ~ 90 DEG C, and Mn is 10000 ~ 40000, Mw is 100,000 ~ 500, and 000, softening temperature T1/2 is 130 ~ 180 DEG C, and gel content is 1 ~ 50%.100-200 part dibasic acid, 100-200 part dibasic alcohol, 1-10 part crosslinking chemical and 1-3 part catalyzer are reacted 4 ~ 10 hours water generated except dereaction by described crosslinked polyester resin at 200 ~ 300 DEG C, then carry out decompression vacuum pumping 2 ~ 6 hours to system; Described dibasic acid is the one in terephthalic acid (TPA), m-phthalic acid, phthalic acid, fumaric acid, maleic acid, hexane diacid or decanedioic acid; Dibasic alcohol is one or more the combination in propoxylated bisphenol, Ethoxylated bisphenol A, ethylene glycol, neopentyl glycol, 1,3-PD, BDO or 1,6-hexanediol; Crosslinking chemical is the one in glycerine, pentaerythrite, trimellitic anhydride or pyromellitic anhydride.Catalyzer can use esterification catalyst well known in the art, as molecular sieve, heteropoly acid, solid super-strong acid, metal-organic complex, organic acid, inorganic salts etc.
Further, the described modified epoxy epoxy group content that dissociates be 0 ~ 60mmol/kg, Tg is 30 ~ 60 DEG C, and softening temperature T1/2 is 60 ~ 110 DEG C.50 ~ 150 parts of epoxy resin, 30 ~ 80 parts of modifier and 1-3 part catalyst mixture react 1 ~ 4 hour at 130 ~ 180 DEG C by described modified epoxy, be warming up to 190 ~ 230 DEG C of insulations 1 ~ 3 hour again, the epoxy radicals that removing is residual, obtains modified epoxy; The epoxide equivalent of described epoxy resin is 50 ~ 500; Described modifier is the one in phenolic compounds or carboxylic acid compound; Described catalyzer is the one in potassium chloride, potassium bromide, potassium iodide, phosphine, phosphorus chloride, phosphonium bromide or iodate phosphorus.
Further, described phenolic compounds is the one in p-phenyl phenol, o-phenyl phenol, australol, 2,4-bis-p-t-butyl phenols, 4-cyclohexylphenol or 4-metoxyphenol; The one of carboxylic acid compound only in benzoic acid, phenylacetic acid, 2,4-mesitylenic acids, enanthic acid or n-nonanoic acid.
The invention also discloses the method for described ink powder binding resin composition, comprise the steps:
(1) dibasic acid selected, dibasic alcohol are reacted 2 ~ 8 hours water generated except dereaction at 150 ~ 250 DEG C, then decompression vacuum pumping is carried out to system and prepare linear polyester in 0.5 ~ 4 hour;
(2) dibasic acid selected, dibasic alcohol and crosslinking chemical are reacted at 200 ~ 300 DEG C the water generated except dereaction for 4 ~ 10 hours, then decompression vacuum pumping is carried out to system and prepare crosslinked polyester resin in 2 ~ 6 hours;
(3) epoxy resin, modifier and catalyst mixture are reacted 1 ~ 4 hour at 130 ~ 180 DEG C, then be warming up to 190 ~ 230 DEG C of insulations 1 ~ 3 hour, the epoxy radicals that removing is residual, obtain modified epoxy;
(4) linear polyester that amount takes step (1), prepared by (2) and (3) as required, crosslinked polyester resin and modified epoxy, mix, mixed 30 ~ the 60min of melting at 150 ~ 200 DEG C, cooling, solidification, fragmentation, obtain binding resin composition.
Advantage of the present invention is: the minimum fixing temperature of the ink powder obtained by this binding resin composition reduces by 15 DEG C, and offset temperatures increases by 10 DEG C, and fixing level increases by 16%, and the fouling resistance degree of image and glossiness increase.
Embodiment:
" part " number mentioned herein is parts by weight.
The preparation 1 of linear polyester
By 150 parts of terephthalic acid (TPA)s and 200 parts of propoxylated bisphenol mixing, add 1 part of tetrabutyl titanate catalyst, potpourri reacts the water removing reaction for 4 hours and generate at 220 DEG C, then decompression vacuum pumping is carried out 1 hour to reaction system, vacuum tightness remains on 100 ~ 200Pa, be obtained by reacting light yellow clear material, be called LPE1.Tg=54℃,Mn=3500,Mw=28000,T
1/2=115℃。LEP is linear polyethylene resin.
The preparation 2 of linear polyester
100 parts of fumaric acid and 180 parts of Ethoxylated bisphenol A are mixed, add 1.5 parts of tetrabutyl titanate catalyst, potpourri reacts the water removing reaction for 5 hours and generate at 200 DEG C, then decompression vacuum pumping is carried out 1 hour to reaction system, vacuum tightness remains on 100 ~ 200Pa, be obtained by reacting light yellow clear material, be called LPE2.Tg=62℃,Mn=4900,Mw=34000,T
1/2=120℃。
The preparation 3 of linear polyester
By 100 parts of hexane diacids and 150 parts of ethylene glycol mixing, add 1.5 parts of tetrabutyl titanate catalyst, potpourri reacts the water removing reaction for 8 hours and generate at 250 DEG C, then decompression vacuum pumping is carried out 4 hours to reaction system, vacuum tightness remains on 100 ~ 200Pa, be obtained by reacting light yellow clear material, be called LPE3.Tg=60℃,Mn=4000,Mw=30000,T
1/2=120℃。
The preparation 4 of linear polyester
By 150 parts of hexane diacids and 130 parts of ethylene glycol mixing, add 1 part of tetrabutyl titanate catalyst, potpourri reacts the water removing reaction for 2 hours and generate at 150 DEG C, then decompression vacuum pumping is carried out 0.5 hour to reaction system, vacuum tightness remains on 100 ~ 200Pa, be obtained by reacting light yellow clear material, be called LPE4.Tg=50℃,Mn=3000,Mw=20000,T
1/2=100℃。
The preparation 5 of linear polyester
By 150 parts of fumaric acid and 130 parts of ethylene glycol mixing, add .1.5 part tetrabutyl titanate catalyst, potpourri reacts the water removing reaction for 6 hours and generate at 200 DEG C, then decompression vacuum pumping is carried out 3 hours to reaction system, vacuum tightness remains on 100 ~ 200Pa, be obtained by reacting light yellow clear material, be called LPE5.Tg=40℃,Mn=1000,Mw=8000,T
1/2=140℃。
The preparation 6 of linear polyester
By 100 parts of fumaric acid and 200 parts of ethylene glycol mixing, add .1.5 part tetrabutyl titanate catalyst, potpourri reacts the water removing reaction for 4 hours and generate at 180 DEG C, then decompression vacuum pumping is carried out 2 hours to reaction system, vacuum tightness remains on 100 ~ 200Pa, be obtained by reacting light yellow clear material, be called LPE6.Tg=70℃,Mn=50000,Mw=40000,T
1/2=80℃。
The preparation 1 of cross-linked polyester
By 100 parts of fumaric acid, 150 parts of propoxylated bisphenols, 40 parts of neopentyl glycols, 10 parts of trimellitic anhydride mixing, add 1.5 parts of tetrabutyl titanate catalyst, potpourri reacts the water removing reaction for 3 hours and generate at 230 DEG C, then decompression vacuum pumping is carried out 1.5 hours to reaction system, vacuum tightness remains on 100 ~ 200Pa, be obtained by reacting light yellow clear material, be called GPE1.Tg=75 DEG C, Mn=25000, Mw=300,000, T
1/2=161 DEG C, gel content is 35%.GPE is cross-linked polyester.
The preparation 2 of cross-linked polyester
By 100 parts of fumaric acid, 130 parts of Ethoxylated bisphenol A, 30 parts of ethylene glycol, 8 parts of pentaerythrite mixing, add .1.5 part tetrabutyl titanate catalyst, potpourri reacts the water removing reaction for 4 hours and generate at 240 DEG C, then decompression vacuum pumping is carried out 2 hours to reaction system, vacuum tightness remains on 100 ~ 200Pa, be obtained by reacting light yellow clear material, be called GPE2.Tg=82 DEG C, Mn=40000, Mw=500,000, T
1/2=169 DEG C, gel content is 50%.
The preparation 3 of cross-linked polyester
By 120 parts of hexane diacids, 80 parts of decanedioic acid 100 part 1, ammediol, 70 part 1,4-butylene glycol, 5 parts of trimellitic anhydride mixing, add 1 part of tetrabutyl titanate catalyst, potpourri reacts the water removing reaction for 8 hours and generate at 250 DEG C, and then carry out decompression vacuum pumping 4 hours to reaction system, vacuum tightness remains on 100 ~ 200Pa, be obtained by reacting light yellow clear material, be called GPE3.Tg=90 DEG C, Mn=40000, Mw=100,000, T
1/2=130 DEG C, gel content is 1%.
The preparation 4 of cross-linked polyester
By 100 parts of m-phthalic acids, 100 parts of phthalic acids, 130 parts of Ethoxylated bisphenol A, 50 parts of ethylene glycol, 8 parts of trimellitic anhydride mixing, add 1.5 parts of tetrabutyl titanate catalyst, potpourri reacts the water removing reaction for 4 hours and generate at 210 DEG C, then decompression vacuum pumping is carried out 2 hours to reaction system, vacuum tightness remains on 100 ~ 200Pa, be obtained by reacting light yellow clear material, be called GPE4.Tg=55 DEG C, Mn=42000, Mw=150,000, T
1/2=140 DEG C, gel content is 20%.
The preparation 5 of cross-linked polyester
By 120 parts of hexane diacids, 40 parts of phthalic acids, 110 part 1,4-butylene glycol, 5 parts of trimellitic anhydride mixing, add 1 part of tetrabutyl titanate catalyst, potpourri reacts the water removing reaction for 8 hours and generate at 200 DEG C, then decompression vacuum pumping is carried out 2 hours to reaction system, vacuum tightness remains on 100 ~ 200Pa, is obtained by reacting light yellow clear material, is called GPE5.Tg=60 DEG C, Mn=30000, Mw=450,000, T
1/2=160 DEG C, gel content is 40%.
The preparation 6 of cross-linked polyester
By 50 parts of fumaric acid, 50 parts of phthalic acids, 100 parts of propoxylated bisphenols, 40 parts of neopentyl glycols, 10 parts of ethylene glycol mixing, add 2 parts of tetrabutyl titanate catalyst, potpourri reacts the water removing reaction for 7 hours and generate at 220 DEG C, then decompression vacuum pumping is carried out 3 hours to reaction system, vacuum tightness remains on 100 ~ 200Pa, be obtained by reacting light yellow clear material, be called GPE6.Tg=85 DEG C, Mn=35000, Mw=310,000, T
1/2=155 DEG C, gel content is 47%.
The preparation 1 of modified epoxy
By 100 parts of epoxy resin E-44s and 55 parts of p-phenyl phenol mixing, add 1 part of base catalyst KI, potpourri 150 DEG C of reactions 3 hours, then is warming up to 200 DEG C of insulations 2 hours, to remove residual epoxy radicals, obtains light yellow clear material, is called MEP1.Tg=45 DEG C, free epoxy group content is 30mmol/kg, T
1/2=86 DEG C.MEP is modified epoxy.
The preparation 2 of modified epoxy
By 100 parts of epoxy resin E-44s and 50 parts of benzoic acid mixing, add 1. parts of base catalyst KI, potpourri 170 DEG C of reactions 3 hours, then is warming up to 200 DEG C of insulations 2 hours, to remove residual epoxy radicals, obtains light yellow clear material, is called MEP2.Tg=39 DEG C, free epoxy group content is 35mmol/kg, T
1/2=78 DEG C.
The preparation of binding resin composition
Embodiment 1
By 80 parts of LPE1,10 parts of GPE1 and 10 part MEP1 at 150 DEG C of abundant melting mixing 60min, cooling, solidification, broken, fine powder, obtain binding resin composition 1.
Embodiment 2
By 80 parts of LPE2,10 parts of GPE1 and 10 part MEP1 at 175 DEG C of abundant melting mixing 50min, cooling, solidification, broken, fine powder, obtain binding resin composition 2.
Embodiment 3
By 70 parts of LPE1,15 parts of GPE1 and 15 part MEP1 at 200 DEG C of abundant melting mixing 30min, cooling, solidification, broken, fine powder, obtain binding resin composition 3.
Embodiment 4 ~ embodiment 17 is filled a prescription in table 1, and table 2, preparation method is with embodiment 2.
Embodiment 1 ~ embodiment 17 is prepared into ink powder respectively, investigates minimum fixing temperature and the offset temperatures of ink powder, the fixing level of image and image quality.
Table 1. resin composition formula and ink powder photocopying effect evaluation result
Table 1 summarizes the resin formula of embodiment 1 ~ embodiment 8 ink powder and corresponding photocopying effect evaluation result.As can be seen from the table, when the amount of MEP1 is increased to 10 parts, the minimum fixing temperature of ink powder can be reduced, and very little on the impact of offset temperatures, and fixing level increases, and image quality improves.When the amount of MEP1 and GPE1 is increased to 15 parts simultaneously, find that minimum fixing temperature reduces by 9 DEG C, offset temperatures improves 4 DEG C, and fixing level improves 10%, and image quality is excellent.When further the amount of MEP1 and GPE1 being increased to 20 parts, find that minimum fixing temperature reduces by 14 DEG C, offset temperatures improves 10 DEG C, and fixing level improves 13%, and image quality is excellent.Can draw thus, increase the minimum fixing temperature that not only can reduce ink powder while modified epoxy and cross-linked polyester amount, improve offset temperatures, can also fixing level be increased, obtain excellent image quality.
In addition, also can find from table 1, contrast linear polyester LPE1 and LPE2, LPE1 molecular weight is smaller, and its minimum fixing temperature is on the low side, does not also affect the offset temperatures of ink powder, and the image fixing firmness obtained is better than the larger LPE2 of molecular weight.So in above-mentioned formula, be more preferably the linear polyester LPE1 that molecular weight is relatively smaller.
For the modified epoxy of the cross-linked polyester and different Tg of investigating different molecular weight is further on the impact of ink powder performance, compared for formula and the ink powder photocopying effect of the resin combination of example 9-example 17.
Table 2. resin composition formula and ink powder photocopying effect evaluation result
From embodiment 9, embodiment 10 can be found out, when the amount of MEP1 is increased to 25 parts, when the amount of GPE1 is 15 parts, minimum fixing temperature reduces further, but image occurs stained on a small quantity.When cross-linked polyester makes GPE2 into by GPE1, offset temperatures increases to some extent, but the glossiness of image is deteriorated, and does not improve the image phenomenon of book contamination in example 15 simultaneously.Same in example 16, when adding cross-linked polyester GPE2, the glossiness of image is also deteriorated.This illustrates for cross-linked polyester, should not select the resin that gel content and molecular weight are too large.
When the amount of MPE1 is 25 parts, when the amount of GPE1 is 20 parts, minimum fixing temperature is 94 DEG C, and offset temperatures is 192 DEG C, and fixing level is 98%, and the picture quality obtained is better.But when the amount of MPE1 is increased to 30 parts, when the amount of GPE1 is 25 parts, the stained increase of image, glossiness is deteriorated.
Comparative example's 13 ~ embodiment 17, when the addition of GPE1 and MEP2 is respectively 10 and 15 parts, the picture quality obtained is better.When the addition of MEP2 is increased to 20 parts, even if when the amount of GPE1 is increased to 20 or 25 parts, the stained of image still can increase.Illustrate that its addition can not be too many for the lower modified epoxy MEP2 of molecular weight, if add excessive, the stained of image will increase.
As can be seen from above-mentioned example, ink powder binding resin composition of the present invention is used in ink powder, can have low fixing temperature, high offset temperatures, excellent fixing level and good image quality simultaneously.
Above example is the embodiment in order to this patent is described, in the application not as restriction.