CN102540715A - Flexible photoresin plate allowing for easy viscosity reduction - Google Patents
Flexible photoresin plate allowing for easy viscosity reduction Download PDFInfo
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Abstract
The invention discloses a flexible photoresin plate allowing for easy viscosity reduction, which comprises 50 to 95 weight percent of a thermoplastic elastomer, 1 to 20 weight percent of mixture of photocrosslinking ethenyl unsaturated monomers, 0.01 to 5 weight percent of photoinitiator or photoinitiator system and 5 to 25 weight percent of aid, wherein the thermoplastic elastomer at least contains one compound with an A1-B1-C1-A1 structure, A1 is a polymerization monoaryl alkane monomer, B1 is a polymerization alkadiene monomer, C1 is a polymerization alkadiene monomer with a structure different from that of B1, the mass percentage content of A1 in the A1-B1-C1-A1 molecular structure is 17 to 30 percent, the weight-average molecular weight of A1 is 2,000 to 30,000, and the weight-average molecular weight B1 and the weight-average molecular weight of C1 are between 50,000 and 200,000. The flexible photoresin plate made of the photosensitive components has low viscosity and the viscosity reduction time in a plate post processing process is short.
Description
Technical field
The invention belongs to the flexible photosensitive resin plate technical field, be specifically related to that a kind of viscosity is little, remove the sticking flexible photosensitive resin plate that is easy in the plate aftertreatment process.
Background technology
At present, flexible photosensitive resin plate is widely used in the printing of easy deformation such as carton, flexible packaging, label or softer stock.
Usually; The film that will have pattern or literal is placed on the unexposed flexographic plate that contains the photosensitive elastomer body, ultraviolet exposure, and the place that film is transparent sees through ultraviolet light; Decomposition of initiator in the photosensitive elastomer body becomes free radical, and the initiation crosslinkable monomers is reacted and solidified.Do not see through ultraviolet zone cross-linking reaction can not take place, utilize the difference of their solubleness in developer solution, flushing is developed and is obtained containing the relief image of character pattern.Plate after the development goes to glue through super-dry, and the complete polymerization of photographic layer is guaranteed in post-exposure.The plate that makes is fixed on the cylinder of flexible printing press, can prepare printing.
Along with the development of gentle platemaking technology, flexible resin version CTP arises at the historic moment, and does not need film, can realize plate-making.It is on traditional dull and stereotyped plate or sleeve; With post be coated with, encircle be coated with, the ablation layer of method and technology such as spraying coating one deck sensible heat, ablate through superlaser, form so-called film function; Accomplish the plate-making process as common flexible photosensitive resin plate then, last machine printing.
Common plate, especially 1.70mm or 1.14mm thickness are used to realize high-grade meticulous flexible resin version of printing, and require the plate surface not to be clamminess, otherwise in the printing process, the shredded paper bits are bonded at the forme surface, cause printing ink to be difficult to transfer on the stock.When serious, the shredded paper bits are bonded at the anti-white part of forme, cause on the printing dirtyly, need to shut down and clean the printing of could starting shooting again behind the forme, waste paper and man-hour.
And its plate surface viscosity of existing product is bigger, and is not ideal enough, for solving the tough problem of plate; U.S. Pat 4725528 disclosed technology; Plate was immersed in 0.4% the bromine aqueous solution 5 minutes, and plate put into solution neutralizations such as sodium thiosulfate again, plate surface, dry back is sticking.This technology is because of using bromine water, and toxicity is big and environmental pollution is strong.
Summary of the invention
The objective of the invention is to solve the problems referred to above that exist in the prior art, a kind of flexible photosensitive resin plate of gluing of going easily is provided.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is following:
The flexible photosensitive resin plate that glues of going easily of the present invention, the sensitization component of this photopolymer plate comprises:
(A) thermoplastic elastomer of 50-95wt%; This thermoplastic elastomer contains the compound that a kind of structure is A1-B1-C1-A1 at least, and wherein A1 is single aromatic yl paraffin monomer of polymerization, and B1 is the diolefinic monomer of polymerization; C1 is the diolefinic monomer of the chemical constitution polymerization different with B1; A1 quality percentage composition in the A1-B1-C1-A1 molecular structure is 17%-30%, and the A1 weight-average molecular weight is 2000-30000, is preferably 2000-30000.B1, C1 weight-average molecular weight are 50000-200000; Be preferably 50000-200000.
(B) 1-20wt% can photo-crosslinking the unsaturated vinyl monomer potpourri;
(C) light trigger of 0.01-5wt% or light initiation system;
(D) auxiliary agent of 5-25wt%.
Single aromatic yl paraffin monomer A 1 of described polymerization is an AMS, styrene, and vinyltoluene, p-methylstyrene, vinyl naphthalene is in the butylstyrene any one.
The diolefinic monomer B1 of described polymerization is 1,4-butadiene, 1,3-butadiene, isoprene, any one in 1-phenyl-1,3-butadiene equiconjugate diene.
The diolefinic monomer B2 of described polymerization is 1,4-butadiene, 1,3-butadiene, isoprene, any one in 1-phenyl-1,3-butadiene equiconjugate diene.
Described unsaturated vinyl monomer potpourri that can photo-crosslinking, contain following three kinds of unsaturated vinyl monomers at least:
(b1) mono-vinyl alicyclic epoxy compound unsaturated monomer that can photo-crosslinking, its weight accounts for the 2-15% of unsaturated vinyl monomer potpourri;
(b2) divinyl unsaturated monomer that can photo-crosslinking, its weight accounts for the 30-80% of unsaturated vinyl monomer potpourri;
(b3) can photo-crosslinking contain the unsaturated vinyl monomer more than three, its weight accounts for the 5-20% of unsaturated vinyl monomer potpourri.
Described mono-vinyl alicyclic epoxy compound unsaturated monomer structural formula that can photo-crosslinking is:
In the formula, R
1Be hydrogen atom or methyl, R
2Be methine, propylidyne, butylidyne, inferior methylol, the ester group that contains six ring-types or hydroxyl substituent, R
3Be five yuan or six-membered cyclic alkane substituting group, R
4Be hydrogen atom or methyl.
Described divinyl unsaturated monomer is 1; Ammediol two (methyl) acrylic ester, 1; 4-butylene glycol two (methyl) acrylic ester, 1; 5-pentanediol two (methyl) acrylic ester, 1; 6-hexanediol two (methyl) acrylic ester, 1; 9-nonanediol two (methyl) acrylic ester, triethylene Glycol two (methyl) acrylic ester, four condensed ethandiol two (methyl) acrylic ester, five condensed ethandiol two (methyl) acrylic ester, propylene glycol diacrylate, tripropylene glycol two (methyl) acrylic ester, four contract propylene glycol two (methyl) acrylic ester, neopentylglycol diacrylate, PDDA, phthalic acid tripropylene glycol diacrylate, ethoxylated bisphenol a diacrylate, 2, at least a in 2-two (p-hydroxybenzene)-propane two (methyl) acrylic ester, pentaerythrite two (methyl) acrylic ester, dihydroxy methylpropane two (methyl) acrylic ester.
Described the unsaturated vinyl monomer more than three of containing that can photo-crosslinking is in ethoxylated trimethylolpropane triacrylate, glycerol propoxylate triacrylate, trimethylolpropane tris (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester, dipentaerythritol five acrylic ester or the two-trimethylolpropane tetra-acrylate any one.
Thermoplastic elastomer of the present invention contains the compound that a kind of structure is A1-B1-C1-A1 at least, also can two or more structures mix, and also can mix with other thermoplastic elastomers such as SIS, SBS.
The weight of thermoplastic elastomer accounts for the 50-95% of flexible photosensitive resin plate sensitization component general assembly (TW), preferred 55-93.99%.
The above-mentioned detailed example of mono-vinyl alicyclic epoxy compound unsaturated monomer M-1 that can photo-crosslinking is stated structural formula as follows, but the present invention is not limited to the structural formula of following sequence number 1-4.
(sequence number 1)
(sequence number 2)
(sequence number 3)
(sequence number 4)
Flexible photosensitive resin plate sensitization component contains initiating agent or initiator system, can be that benzophenone, rice are sneered ketone, 4-acetoxyl group-4
,-diethylamide benzophenone, benzoin ethyl ether, Alpha-hydroxy cumene ketone, Alpha-hydroxy cyclohexyl benzene ketone, 2-phenyl-2; 2-dimethoxy acetyl benzophenone, 2-tertiary butyl anthraquinone, isopropyl thioxanthone, (morpholinyl benzoyl) 1-six base 1,1 (dimethylamino) propane, benzil, benzoin etc.Initiating agent or primosome account for the 0.01-5% of flexible photosensitive resin plate sensitization component general assembly (TW).
Can also add other auxiliary agents such as plastifier, antioxidant, hot suppressant, release agent, levelling agent, dyestuff in the flexible photosensitive resin plate sensitization component.Plastifier can be white oil, low molecular weight liquid polybutadiene, low molecular weight liquid polyisoprene, naphthenic oil, rapeseed oil, Methyl Benzene-o-dicarboxylate, ethyl phthalate, butyl phthalate, AMS-styrene oligomer etc.The weight of plastifier and other adjuvant accounts for the 5-25% of photopolymer plate sensitization component general assembly (TW).
Unsaturated vinyl monomer, initiating agent or initiator system, the plastifier etc. of above-mentioned thermoplastic elastomer of the present invention, photo-crosslinking were mixed 10 minutes in 110～150 ℃ of Banbury mixeies; The mould of different-thickness is put in taking-up; The two sides is compound PET film respectively, and 20～150 ℃ of temperature, hot pressing is 180 seconds under pressure 0.15～14MPa with vulcanizing press; Obtain flexible photosensitive resin plate after the cooling, plate thickness is 1.14mm～7.00mm.Perhaps in extruder 110-160 ℃ mixing 2～5 minutes down, the sensitization component is extruded from die head, through stack; Be calendered to required thickness; The compound PET film on the two sides of sensitization component perhaps covers PET earlier in the one side of sensitization component, after supercooling simultaneously; Get another side in the sensitization component again and cover the PET film, cut into and require size.
The above-mentioned sensitization component that obtains after normal temperature is placed a week, can be tested the surface viscosity size of plate and the assessment plate goes the sticking time in the processed of back length.And then the performance of evaluation plate.
With embodiments of the invention 1-4 and comparative example 1-3; Be cut into the strip of 2cm * 20cm; Throw off film PET; 30 ℃ of following applying adhesive tapes on laminating machine are guaranteed the overlay film constant pressure of the adhesive surface of sensitization component and adhesive tape, then at FPT-F1 friction factor/peel off appearance (the Jinan blue light is dynamo-electric) to go up the cohesive force between test sensitization component and the adhesive tape.Evaluation criterion: the adhesive surface peeling force of sensitization component and adhesive tape is less than 30g/cm, and space of a whole page viscosity is little, uses goodly, is designated as " ☆ "; The adhesive surface peeling force of sensitization component and adhesive tape is at 30～50 g/cm, and space of a whole page viscosity is less, uses better, is designated as " ▲ "; The adhesive surface peeling force of sensitization component and adhesive tape is at 50～100g/cm, and space of a whole page viscosity is big, uses generally, is designated as " ◎ "; The adhesive surface peeling force of sensitization component and adhesive tape is greater than 100g/cm, and space of a whole page viscosity is big, can not use, and is designated as " ● ".
With embodiments of the invention 1-10 and comparative example 1-3, be cut into the strip of 5cm * 10cm, throw off film PET; Went up face exposure 10 minutes at flexible plate making machine KY1320 (Guangzhou white clouds science and trade); In zellon/normal butyl alcohol (volume ratio 3:1), washed version 5 minutes, dried 1.5 hours for 60 ℃.Going under the sticking fluorescent tube of wavelength 280nm, spacing 5cm removes sticking different time, and with the positive crooked contact of version, under the no external force, the space of a whole page of contact naturally separately shows that the space of a whole page is not sticking.Evaluation criterion: go the sticking time shorter better.
Evaluation result is seen table 1.
Can find out that from table 1 adopt sensitization component of the present invention, the plate surface viscosity is little, go the sticking time shorter, improve plate-making efficient, the user is convenient to use.
The viscosity of table 1 embodiment and comparative example sensitization component size with go the sticking time
Embodiment
Embodiment 1
(1) the sensitization component of flexible resin version consists of:
(A) thermoplastic elastomer:
Structural formula is the compound of A1-B1-C1-A1, and wherein A1 is a polystyrene, and B1 is a polyisoprene, and C1 is a polybutadiene.Thermoplastic elastomer SIBS, weight-average molecular weight 190,000, PS weight content 18.5%, PS weight-average molecular weight 1.5 ten thousand, PI weight-average molecular weight 70,000, PB weight-average molecular weight 90,000, company is risen by section, 500 grams;
(B) unsaturated vinyl monomer potpourri that can photo-crosslinking:
The compound of (sequence number 3), 3,4-epoxycyclohexyl methyl acrylate (the Shanghai thing is competed chemical company) 10 grams;
Hexanediol dimethacrylate (Tianjin proud son of heaven chemical industry company limited) 150 grams;
Ethoxylated trimethylolpropane triacrylate (Tianjin proud son of heaven chemical industry company limited) 40 grams;
(C) light trigger or light initiation system:
651 light triggers (Jingjiang grand safe chemical industry company limited), 50 grams;
(D) auxiliary agent:
No. 7 white oils of plastifier (generation side, Tianjin chemical industry) 230 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 (BASF) 0.05 gram.
(2) preparation method of flexible resin version:
With above-mentioned thermoplastic elastomer SIBS 500 grams, the present invention's's (sequence number 3) compound 10 grams, hexanediol dimethacrylate 150 grams, ethoxylated trimethylolpropane triacrylate 40 grams, 651 light triggers, 50 grams, No. 7 white oils of plastifier 230 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram, on KY one 3200 Banbury mixeies (the thick street of Dongguan City is opened and ground plant equipment factory) 120 ℃ mixing 10 minutes, discharging; The sensitization material is placed the mould of 3.94mm, and it respectively covers one deck PET film up and down, forms sandwich structure; Use 120 ℃ of pressing plates of vulcanizing press then, hot pressing is 3 minutes under the 7MP pressure, after cooling; Taking-up obtains the sensitization component, is used for test.
Embodiment 2
(1) the sensitization component of flexible resin version consists of:
(A) thermoplastic elastomer:
Structural formula is the compound of A1-B1-C1-A1, and wherein A1 is a polystyrene, and B1 is a polyisoprene, and C1 is a polybutadiene.Thermoplastic elastomer SIBS, weight-average molecular weight 190,000, PS weight content 18.5%, PS weight-average molecular weight 1.5 ten thousand, PI weight-average molecular weight 70,000, PB weight-average molecular weight 90,000, company is risen by section, 500 grams;
(B) unsaturated vinyl monomer potpourri that can photo-crosslinking:
The compound of (sequence number 3), 3,4-epoxycyclohexyl methyl acrylate 30 grams;
Hexanediol dimethacrylate 130 grams;
Ethoxylated trimethylolpropane triacrylate 40 grams;
(C) light trigger or light initiation system:
651 light triggers, 50 grams;
(D) auxiliary agent:
No. 7 white oils of plastifier 230 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram.
(2) preparation method of flexible resin version:
With above-mentioned thermoplastic elastomer SIBS 500 grams, the present invention's's (sequence number 3) compound 30 grams, hexanediol dimethacrylate 130 grams, ethoxylated trimethylolpropane triacrylate 40 grams, 651 light triggers, 50 grams, No. 7 white oils of plastifier 230 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram, on KY one 3200 Banbury mixeies 120 ℃ mixing 10 minutes, discharging; The sensitization material is placed the mould of 3.94mm, and it respectively covers one deck PET film up and down, forms sandwich structure; Use 120 ℃ of pressing plates of vulcanizing press then, hot pressing is 3 minutes under the 7MP pressure, after cooling; Taking-up obtains the sensitization component, is used for test.
Embodiment 3
(1) the sensitization component of flexible resin version consists of:
(A) thermoplastic elastomer:
Structural formula is the compound of A1-B1-C1-A1, and wherein A1 is a polystyrene, and B1 is a polyisoprene, and C1 is a polybutadiene.Thermoplastic elastomer SIBS, weight-average molecular weight 190,000, PS weight content 18.5%, PS weight-average molecular weight 1.5 ten thousand, PI weight-average molecular weight 70,000, PB weight-average molecular weight 90,000, company is risen by section, 400 grams;
Thermoplastic elastomer SIS, weight-average molecular weight 150,000, PS weight content 25%, PS weight-average molecular weight 1.5 ten thousand, Yueyang petrochemical industry 100 grams
(B) unsaturated vinyl monomer potpourri that can photo-crosslinking:
The compound of (sequence number 3), 3,4-epoxycyclohexyl methyl acrylate 30 grams;
Hexanediol dimethacrylate 130 grams;
Ethoxylated trimethylolpropane triacrylate 40 grams;
(C) light trigger or light initiation system:
651 light triggers, 50 grams;
(D) auxiliary agent:
No. 7 white oils of plastifier 230 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram.
(2) preparation method of flexible resin version:
With above-mentioned thermoplastic elastomer SIBS 400 grams, SIS 100 grams, the present invention's's (sequence number 3) compound 30 grams, hexanediyl ester 130 grams, ethoxylated trimethylolpropane triacrylate 40 grams, 651 light triggers, 50 grams, No. 7 white oils of plastifier 230 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram, on KY one 3200 Banbury mixeies 120 ℃ mixing 10 minutes, discharging; The sensitization material is placed the mould of 3.94mm, and it respectively covers one deck PET film up and down, forms sandwich structure; Use 120 ℃ of pressing plates of vulcanizing press then, hot pressing is 3 minutes under the 7MP pressure, after cooling; Taking-up obtains the sensitization component, is used for test.
Embodiment 4:
(1) the sensitization component of flexible resin version consists of:
(A) thermoplastic elastomer:
Structural formula is the compound of A1-B1-C1-A1, and wherein A1 is a polystyrene, and B1 is a polyisoprene, and C1 is a polybutadiene.Thermoplastic elastomer SIBS, weight-average molecular weight 190,000, PS weight content 18.5%, PS weight-average molecular weight 1.5 ten thousand, PI weight-average molecular weight 70,000, PB weight-average molecular weight 90,000, company is risen by section, 600 grams;
Thermoplastic elastomer SIS, weight-average molecular weight 150,000, PS weight content 25%, PS weight-average molecular weight 1.5 ten thousand, Yueyang petrochemical industry, 100 grams;
(B) unsaturated vinyl monomer potpourri that can photo-crosslinking:
The compound of (sequence number 3), 3,4-epoxycyclohexyl methyl acrylate 15 grams;
Hexanediol dimethacrylate 70 grams;
Ethoxylated trimethylolpropane triacrylate 15 grams;
(C) light trigger or light initiation system:
651 light triggers, 25 grams;
(D) auxiliary agent:
No. 7 white oils of plastifier 155 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram.
(2) preparation method of flexible resin version:
With above-mentioned thermoplastic elastomer SIBS 600 grams, SIS 100 grams; The present invention's's (sequence number 3) compound 15 grams, hexanediol dimethacrylate 70 grams, ethoxylated trimethylolpropane triacrylate 15 grams, 651 light triggers, 25 grams, No. 7 white oils of plastifier 155 grams, 2; 6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram, on KY one 3200 Banbury mixeies 120 ℃ mixing 10 minutes, discharging; The sensitization material is placed the mould of 3.94mm, and it respectively covers one deck PET film up and down, forms sandwich structure; Use 120 ℃ of pressing plates of vulcanizing press then, hot pressing is 3 minutes under the 7MP pressure, after cooling; Taking-up obtains the sensitization component, is used for test.
Embodiment 5
(1) the sensitization component of flexible resin version consists of:
(A) thermoplastic elastomer:
Structural formula is the compound of A1-B1-C1-A1, and wherein A1 is a polystyrene, and B1 is a polyisoprene, and C1 is a polybutadiene.Thermoplastic elastomer SIBS, weight-average molecular weight 210,000, PS weight content 18.0%, PS weight-average molecular weight 1.3 ten thousand, PI weight-average molecular weight 10.4 ten thousand, PB weight-average molecular weight 90,000, company is risen by section, 700 grams;
(B) unsaturated vinyl monomer potpourri that can photo-crosslinking:
The compound of (sequence number 3), 3,4-epoxycyclohexyl methyl acrylate 15 grams;
Hexanediol dimethacrylate 70 grams
Ethoxylated trimethylolpropane triacrylate 15 grams;
(C) light trigger or light initiation system:
651 light triggers, 25 grams
(D) auxiliary agent:
No. 7 white oils of plastifier 155 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram.
(2) preparation method of flexible resin version:
Compound 15 grams, hexanediol dimethacrylate 70 grams, ethoxylated trimethylolpropane triacrylate 15 grams, 651 light triggers, 25 grams with above-mentioned thermoplastic elastomer SIBS 700 grams, the present invention's (sequence number 3); No. 7 white oils of plastifier 155 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram, on extruder 150 ℃ mixing 3 minutes, from the die head discharging; 130 ℃ of material temperature, getting into the gap is the stack calendering of 3.90mm, up and down respectively cover one deck PET film with the sensitization component this moment; After cooling, obtaining thickness is the sensitization component of 3.94mm, is used for test.
Embodiment 6
(1) the sensitization component of flexible resin version consists of:
(A) thermoplastic elastomer:
Structural formula is the compound of A1-B1-C1-A1, and wherein A1 is a polystyrene, and B1 is a polyisoprene, and C1 is a polybutadiene.Thermoplastic elastomer SIBS, weight-average molecular weight 210,000, PS weight content 18.0%, PS weight-average molecular weight 1.3 ten thousand, PI weight-average molecular weight 10.4 ten thousand, PB weight-average molecular weight 90,000, company is risen by section, 700 grams;
(B) unsaturated vinyl monomer potpourri that can photo-crosslinking:
The compound of (sequence number 4), 3-methyl-3,4-epoxycyclohexyl propyl acrylate 15 grams;
Hexanediol dimethacrylate 70 grams;
Ethoxylated trimethylolpropane triacrylate 15 grams;
(C) light trigger or light initiation system:
651 light triggers, 25 grams;
(D) auxiliary agent:
No. 7 white oils of plastifier 155 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram.
(2) preparation method of flexible resin version:
With above-mentioned thermoplastic elastomer SIBS 700 grams, the present invention's's (sequence number 4) compound 15 grams, hexanediol dimethacrylate 70 grams, ethoxylated trimethylolpropane triacrylate 15 grams, 651 light triggers, 25 grams, No. 7 white oils of plastifier 155 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram, on extruder 150 ℃ mixing 3 minutes, from the die head discharging; 130 ℃ of material temperature, getting into the gap is the stack calendering of 3.90mm, up and down respectively cover one deck PET film with the sensitization component this moment; After cooling, obtaining thickness is the sensitization component of 3.94mm, is used for test.
Embodiment 7
(1) the sensitization component of flexible resin version consists of:
(A) thermoplastic elastomer:
Structural formula is the compound of A1-B1-C1-A1, and wherein A1 is a polystyrene, and B1 is a polyisoprene, and C1 is a polybutadiene.Thermoplastic elastomer SIBS, weight-average molecular weight 210,000, PS weight content 18.0%, PS weight-average molecular weight 1.3 ten thousand, PI weight-average molecular weight 10.4 ten thousand, PB weight-average molecular weight 90,000, company is risen by section, 700 grams;
(B) unsaturated vinyl monomer potpourri that can photo-crosslinking:
The compound of (sequence number 4), 3-methyl-3,4-epoxycyclohexyl propyl acrylate 5 grams;
Hexanediyl ester 80 grams;
Trimethylolpropane triacrylate (Tianjin proud son of heaven chemical industry company limited) 15 grams;
(C) light trigger or light initiation system:
651 light triggers, 12 grams;
(D) auxiliary agent:
No. 7 white oils of plastifier 172 grams, 2,6-di-t-butyl-4-methoxyl phenol 15.95 grams, Neozapon
Red335 0.05 gram.
(2) preparation method of flexible resin version:
Compound 5 grams, hexanediyl ester 80 grams, trimethylolpropane triacrylate 15 grams with above-mentioned thermoplastic elastomer SIBS 700 grams, the present invention's (sequence number 4); 651 light triggers, 12 grams; No. 7 white oils of plastifier 172 grams, 2,6-di-t-butyl-4-methoxyl phenol 15.95 grams, Neozapon
Red335 0.05 gram, on extruder 150 ℃ mixing 3 minutes, from the die head discharging; 140 ℃ of material temperature, getting into the gap is the stack calendering of 3.90mm, up and down respectively cover one deck PET film with the sensitization component this moment; After cooling, obtaining thickness is the sensitization component of 3.94mm, is used for test.
Embodiment 8
(1) the sensitization component of flexible resin version consists of:
(A) thermoplastic elastomer:
Structural formula is the compound of A1-B1-C1-A1, and wherein A1 is a polystyrene, and B1 is a polyisoprene, and C1 is a polybutadiene.Thermoplastic elastomer SIBS, weight-average molecular weight 210,000, PS weight content 18.0%, PS weight-average molecular weight 1.3 ten thousand, PI weight-average molecular weight 10.4 ten thousand, PB weight-average molecular weight 90,000, company is risen by section, 600 grams;
(B) unsaturated vinyl monomer potpourri that can photo-crosslinking:
The compound of (sequence number 4), 3-methyl-3,4-epoxycyclohexyl propyl acrylate 30 grams;
Hexanediyl ester 100 grams;
Hexanediol dimethacrylate 50 grams;
Trimethylolpropane triacrylate 20 grams;
(C) light trigger or light initiation system:
651 light triggers, 20 grams;
(D) auxiliary agent:
No. 7 white oils of plastifier 160 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram.
(2) preparation method of flexible resin version:
With above-mentioned thermoplastic elastomer SIBS 600 grams, the present invention's's (sequence number 4) compound 30 grams, hexanediyl ester 100 grams, hexanediol dimethacrylate 50 grams, trimethylolpropane triacrylate 20 grams, 651 light triggers, 20 grams, No. 7 white oils of plastifier 160 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram, on extruder 130 ℃ mixing 3 minutes, from the die head discharging; 140 ℃ of material temperature, getting into the gap is the stack calendering of 3.90mm, up and down respectively cover one deck PET film with the sensitization component this moment; After cooling, obtaining thickness is the sensitization component of 3.94mm, is used for test.
Embodiment 9
(1) the sensitization component of flexible resin version consists of:
(A) thermoplastic elastomer:
Structural formula is the compound of A1-B1-C1-A1, and wherein A1 is a polystyrene, and B1 is a polyisoprene, and C1 is a polybutadiene.Thermoplastic elastomer SIBS, weight-average molecular weight 210,000, PS weight content 18.0%, PS weight-average molecular weight 1.3 ten thousand, PI weight-average molecular weight 10.4 ten thousand, PB weight-average molecular weight 90,000, company is risen by section, 700 grams;
(B) unsaturated vinyl monomer potpourri that can photo-crosslinking:
The compound of (sequence number 4), 3-methyl-3,4-epoxycyclohexyl propyl acrylate 20 grams;
Hexanediyl ester 100 grams;
Hexanediol dimethacrylate 50 grams;
Trimethylolpropane triacrylate 30 grams;
(C) light trigger or light initiation system:
651 light triggers, 20 grams;
(D) auxiliary agent:
Kelamayi naphthenic oil KN4010 160 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram.
(2) preparation method of flexible resin version:
With above-mentioned thermoplastic elastomer SIBS 700 grams, the present invention's's (sequence number 4) compound 20 grams, hexanediyl ester 100 grams, hexanediol dimethacrylate 50 grams, trimethylolpropane triacrylate 30 grams, 651 light triggers, 20 grams, Kelamayi naphthenic oil KN4010 160 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram, on extruder 150 ℃ mixing 3 minutes, from the die head discharging; 135 ℃ of material temperature, getting into the gap is the stack calendering of 3.90mm, up and down respectively cover one deck PET film with the sensitization component this moment; After cooling, obtaining thickness is the sensitization component of 3.94mm, is used for test.
Embodiment 10
(1) the sensitization component of flexible resin version consists of:
(A) thermoplastic elastomer:
Structural formula is the compound of A1-B1-C1-A1, and wherein A1 is a polystyrene, and B1 is a polyisoprene, and C1 is a polybutadiene.Thermoplastic elastomer SIBS, weight-average molecular weight 210,000, PS weight content 18.0%, PS weight-average molecular weight 1.3 ten thousand, PI weight-average molecular weight 10.4 ten thousand, PB weight-average molecular weight 90,000, company is risen by section, 700 grams;
Yueyang petrochemical industry thermoplastic elastomer SIS, weight-average molecular weight 150,000, PS weight content 25%, PS weight-average molecular weight 1.5 ten thousand, 100 grams;
(B) unsaturated vinyl monomer potpourri that can photo-crosslinking:
The compound of (sequence number 4), 3-methyl-3,4-epoxycyclohexyl propyl acrylate 6 grams;
Hexanediyl ester 50 grams;
Hexanediol dimethacrylate 25 grams;
Trimethylolpropane triacrylate 4 grams;
Trimethylol-propane trimethacrylate 15 grams;
(C) light trigger or light initiation system:
651 light triggers, 6 grams;
(D) auxiliary agent:
Kelamayi KN4010 naphthenic oil 84 grams, 2,6-di-t-butyl-4-methoxyl phenol 9.95 grams, Neozapon
Red335 0.05 gram.
(2) preparation method of flexible resin version:
With above-mentioned thermoplastic elastomer SIBS 700 grams, Yueyang petrochemical industry SIS 100 grams, the present invention's's (sequence number 4) compound 6 grams, hexanediyl ester 50 grams, hexanediol dimethacrylate 25 grams, trimethylolpropane triacrylate 4 grams, trimethylol-propane trimethacrylate 15 grams, 651 light triggers, 6 grams, Kelamayi KN4010 naphthenic oil 84 grams, 2,6-di-t-butyl-4-methoxyl phenol 9.95 grams, Neozapon
Red335 0.05 gram, on extruder 150 ℃ mixing 3 minutes, from the die head discharging; 135 ℃ of material temperature, getting into the gap is the stack calendering of 3.9mm, up and down respectively cover one deck PET film with the sensitization component this moment; After cooling, obtaining thickness is the sensitization component of 3.94mm, is used for test.
Comparative example 1
With thermoplastic elastomer SIS 1161 (weight-average molecular weight 230,000; PS weight content 18%; PS weight-average molecular weight 1.8 ten thousand; Company is risen by section) 500 grams, hexanediol dimethacrylate 150 gram, ethoxylated trimethylolpropane triacrylate 50 grams, 651 light triggers, 50 grams, No. 7 white oils of plastifier 230 grams, 2,6-di-t-butyl-4-methoxyl phenol 19.95 grams, Neozapon
Red335 0.05 gram, on KY one 3200 Banbury mixeies (the thick street of Dongguan City is opened and ground plant equipment factory) 120 ℃ mixing 10 minutes, discharging; The sensitization material is placed the mould of 3.94mm, and it respectively covers one deck PET film up and down, forms sandwich structure; Use 120 ℃ of pressing plates of vulcanizing press then, hot pressing is 3 minutes under the 7MP pressure, after cooling; Taking-up obtains the sensitization component, is used for test.
Comparative example 2
With thermoplastic elastomer SIS 1161 (weight-average molecular weight 230,000; PS weight content 18%; PS weight-average molecular weight 1.8 ten thousand) 700 grams, hexanediyl ester 80 grams, trimethylolpropane triacrylate 20 grams; 651 light triggers, 12 grams, No. 7 white oils of plastifier 172 grams, 2,6-di-t-butyl-4-methoxyl phenol 15.95 grams, Neozapon
Red335 0.05 gram, on extruder 150 ℃ mixing 3 minutes, from the die head discharging; 140 ℃ of material temperature, getting into the gap is the stack calendering of 3.90mm, up and down respectively cover one deck PET film with the sensitization component this moment; After cooling, obtaining thickness is the sensitization component of 3.94mm, is used for test.
Comparative example 3
With the flexible plate of the 3.94mm of Taiwan one tame commercially available brand, throw off the upper strata diaphragm, with adhesive tape or pure flush away adherent layer, test the cohesive force of sensitization component and adhesive tape by method of testing of the present invention again and go sticking time size.
Claims (5)
1. one kind is removed the flexible photosensitive resin plate that glues easily, and it is characterized in that: the sensitization component of this photopolymer plate comprises:
(A) thermoplastic elastomer of 50-95wt%; This thermoplastic elastomer contains the compound that a kind of structure is A1-B1-C1-A1 at least, and wherein A1 is single aromatic yl paraffin monomer of polymerization, and B1 is the diolefinic monomer of polymerization; C1 is the diolefinic monomer of the chemical constitution polymerization different with B1; A1 quality percentage composition in the A1-B1-C1-A1 molecular structure is 17%-30%, and the A1 weight-average molecular weight is 2000-30000, and B1, C1 weight-average molecular weight are 50000-200000;
(B) 1-20wt% can photo-crosslinking the unsaturated vinyl monomer potpourri;
(C) light trigger of 0.01-5wt% or light initiation system;
(D) auxiliary agent of 5-25wt%.
2. the flexible photosensitive resin plate that glues of going easily according to claim 1 is characterized in that: described unsaturated vinyl monomer potpourri that can photo-crosslinking, contain following three kinds of unsaturated vinyl monomers at least:
(b1) mono-vinyl alicyclic epoxy compound unsaturated monomer that can photo-crosslinking, its weight accounts for the 2-15% of unsaturated vinyl monomer potpourri;
(b2) divinyl unsaturated monomer that can photo-crosslinking, its weight accounts for the 30-80% of unsaturated vinyl monomer potpourri;
(b3) can photo-crosslinking contain the unsaturated vinyl monomer more than three, its weight accounts for the 5-20% of unsaturated vinyl monomer potpourri.
3. according to the described flexible photosensitive resin plate that glues of going easily of claim 2, it is characterized in that: described mono-vinyl alicyclic epoxy compound unsaturated monomer structural formula that can photo-crosslinking is:
In the formula, R
1Be hydrogen atom or methyl, R
2Be methine, propylidyne, butylidyne, inferior methylol, the ester group that contains six ring-types or hydroxyl substituent, R
3Be five yuan or six-membered cyclic alkane substituting group, R
4Be hydrogen atom or methyl.
4. according to claim 2 or the 3 described flexible photosensitive resin plates that glue of going easily; It is characterized in that: described divinyl unsaturated monomer is 1; Ammediol two (methyl) acrylic ester, 1; 4-butylene glycol two (methyl) acrylic ester, 1; 5-pentanediol two (methyl) acrylic ester, 1; 6-hexanediol two (methyl) acrylic ester, 1; 9-nonanediol two (methyl) acrylic ester, triethylene Glycol two (methyl) acrylic ester, four condensed ethandiol two (methyl) acrylic ester, five condensed ethandiol two (methyl) acrylic ester, propylene glycol diacrylate, tripropylene glycol two (methyl) acrylic ester, four contract propylene glycol two (methyl) acrylic ester, neopentylglycol diacrylate, PDDA, phthalic acid tripropylene glycol diacrylate, ethoxylated bisphenol a diacrylate, 2, at least a in 2-two (p-hydroxybenzene)-propane two (methyl) acrylic ester, pentaerythrite two (methyl) acrylic ester, dihydroxy methylpropane two (methyl) acrylic ester.
5. according to the described flexible photosensitive resin plate that glues of going easily of claim 4, it is characterized in that: described the unsaturated vinyl monomer more than three of containing that can photo-crosslinking is in ethoxylated trimethylolpropane triacrylate, glycerol propoxylate triacrylate, trimethylolpropane tris (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester, dipentaerythritol five acrylic ester or the two-trimethylolpropane tetra-acrylate any one.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010106143049A CN102540715A (en) | 2010-12-30 | 2010-12-30 | Flexible photoresin plate allowing for easy viscosity reduction |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010106143049A CN102540715A (en) | 2010-12-30 | 2010-12-30 | Flexible photoresin plate allowing for easy viscosity reduction |
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| CN102540715A true CN102540715A (en) | 2012-07-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102854747A (en) * | 2012-09-28 | 2013-01-02 | 乐凯华光印刷科技有限公司 | Flexible photopolymer plate with small plate surface viscosity |
| CN104151940A (en) * | 2014-08-19 | 2014-11-19 | 内蒙古工业大学 | Inkjet UV ink |
| CN104723717A (en) * | 2013-12-19 | 2015-06-24 | 乐凯华光印刷科技有限公司 | Computer-to-plate flexible plate and production method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1698015A (en) * | 2003-04-29 | 2005-11-16 | 克拉通聚合物研究有限公司 | Photopolymerizable compositions and flexographic printing plates derived therefrom |
| WO2010116743A1 (en) * | 2009-04-10 | 2010-10-14 | 日本電子精機株式会社 | Photosensitive resin composition for flexographic printing having excellent solvent resistance |
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2010
- 2010-12-30 CN CN2010106143049A patent/CN102540715A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1698015A (en) * | 2003-04-29 | 2005-11-16 | 克拉通聚合物研究有限公司 | Photopolymerizable compositions and flexographic printing plates derived therefrom |
| WO2010116743A1 (en) * | 2009-04-10 | 2010-10-14 | 日本電子精機株式会社 | Photosensitive resin composition for flexographic printing having excellent solvent resistance |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102854747A (en) * | 2012-09-28 | 2013-01-02 | 乐凯华光印刷科技有限公司 | Flexible photopolymer plate with small plate surface viscosity |
| CN102854747B (en) * | 2012-09-28 | 2017-06-06 | 乐凯华光印刷科技有限公司 | The small flexible photosensitive resin plate of plate surface viscosity |
| CN104723717A (en) * | 2013-12-19 | 2015-06-24 | 乐凯华光印刷科技有限公司 | Computer-to-plate flexible plate and production method thereof |
| CN104723717B (en) * | 2013-12-19 | 2017-08-25 | 乐凯华光印刷科技有限公司 | A kind of flexographic plate of CTP and preparation method thereof |
| CN104151940A (en) * | 2014-08-19 | 2014-11-19 | 内蒙古工业大学 | Inkjet UV ink |
| CN104151940B (en) * | 2014-08-19 | 2016-09-28 | 内蒙古工业大学 | A kind of ink-jet UV ink |
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Application publication date: 20120704 |