CN102079961B - Ultraviolet curing adhesive - Google Patents
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- CN102079961B CN102079961B CN 201010551609 CN201010551609A CN102079961B CN 102079961 B CN102079961 B CN 102079961B CN 201010551609 CN201010551609 CN 201010551609 CN 201010551609 A CN201010551609 A CN 201010551609A CN 102079961 B CN102079961 B CN 102079961B
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Abstract
The invention discloses an ultraviolet curing adhesive comprising a resin main body, a dissolvent, an ultraviolet light initiator and an addition agent, wherein the resin main body is composed of a resin R and a resin H; the R resin is an active polyurethane acrylic resin with a main chain containing a polyether structure and a branch chain containing a vinyl optical active group as well as with a lower molecular weight; and the H resin is an inert polyurethane acrylic resin with a main chain containing a polydiene and aryloxide structure and with a relatively higher molecular weight. The adhesive contains no monomer or prepolymer, has high softening point, can be precoated on a base material, has super strong cohesive force on a high-oilness contact surface and has characteristics of high-temperature resistance, small internal stress and good flexibility.
Description
Technical field
The invention belongs to flexible resin platemaking technology field, be specifically related to a kind of ultraviolet light polymerization caking agent.
Background technology
In recent years, flexible photosensitive resin plate was widely used in the printing of yielding or softer stock such as carton, soft packaging, label because of advantage such as use the water-based inks environmental protection, the material of undertaking the printing of is extensive, pressrun is high, the seal machine is simple and easy to make up.At present external flexible photosensitive resin plate technology is ripe, and many external major companies such as Du Pont, Asahi Chemical Industry, Medellin, rich woods top grade are all released product, and domestic have only Lekai two glue to release product, and scale operation.The flexible photosensitive resin plate exploitation is world's printing plate hot of research and development always.
Usually, the structure of flexible photosensitive resin plate is followed successively by base material, adhesive linkage, elastomerics and protective membrane from bottom to top.The effect of adhesive linkage is that the photosensitive elastomer body is fixed on the base material firmly, guarantees the elastomerics dimensional stabilizing, and picture and text are indeformable; Guarantee that strong shearing force that elastomerics and base material can be when not printing and peeling force peel off and come off.
Produce qualified flexographic plate product, adhesive linkage must solve a following main difficult problem:
1, a high oiliness interface bonding difficult problem: fully mixing for the ease of elastomerics when flexographic plate is produced, added a large amount of fourth oil, naphthenic oil more than 20% in the elastomer layer, oils such as silicone oil cause the bonding difficulty of high oiliness elastomerics.
2, flexible fit problem between elastomerics, tack coat, the base material: after the flexographic plate exposure, elastomerics, tack coat, base material three should have certain snappiness, and minimum subzero 30 ℃ are not chapped when curling, indeformable, do not come off.
3, initial bonding strength problem: when flexographic plate was produced, the plate without exposure will have certain initial bonding strength between elastomerics and the base material, occurred to guarantee problems such as plate is out of shape, comes off in cutting, examine processes such as version, packing, transportation.
4, internal stress problem behind the ultraviolet light polymerization: behind the uv-exposure of plate when plate-making, caking agent is crosslinked, must shrink the generation internal stress, solve long-time uv-exposure internal stress shrink cause that plate curls, distortion, bonding force sharply descends even come off problem.
5, printing process bonding force problem: plate should produce powerful bonding force behind uv-exposure, and the plate that makes is fixed on the cylinder of flexible printing press, strong shearing force and peeling force in the time of resisting printing, and assurance elastomerics and base material are not peeled off and are come off.
6, the high temperature resistant problem of caking agent: elastomerics melting temperature 100-130 degree when flexographic plate is produced, caking agent will solve high temperature resistant problem.
7, coating process problem: in order to reduce the variable factor that flexographic plate is produced, caking agent need be coated on the base material standby in advance, and the caking agent softening temperature should be much higher than room temperature, and is tack-free after the drying, and base material can store in rolling, has resistance to compression, adhesion ability.
8, stability problem: base material precoated layer and production plate should have 18 months quality stability.
Be head it off, introduce a kind of thermosetting polyurethane resin among the Mitsui Chemicals JP01115/2000, but snappiness be too poor, easily be full of cracks causes elastomerics and base material to come off; Te Kaiping 1-283557 has introduced bonding with between elastomerics and the support, complicated operation; US Patent No. 4917990 discloses the adhesive linkage that coating contains chlorosulfonated polyethylene, but bonding force can descend along with the increase of exposure.The spy opens and has introduced a kind of moisture curing layer, industrialization difficulty among the 2000-155410; European patent EP 1209524A1 discloses and has been coated with the solution that contains polyvalent alcohol and vulcabond on the base material, but set time is long, the industrial implementation difficulty; WO2004/092841 discloses the bonding method of direct use double-sided adhesive, but error is big, operational difficulty.
Summary of the invention
The objective of the invention is to solve the above-mentioned problems in the prior art, a kind of ultraviolet light polymerization caking agent for the production of flexible resin version is provided.
For achieving the above object, the present invention adopts following technical scheme:
Ultraviolet light polymerization caking agent of the present invention, formed by resin body, solvent, ultraviolet initiator and auxiliary agent, its resin body is formed by containing the inertia polyurethane acrylic resin H that polyether structure active polyurethane acrylic resin R and main chain have polydiene and aryl oxide structure, and the weight ratio of resin R and resin H is 1:10-10:1 in the caking agent.
The resin matrix of described resin R obtains by vulcabond and dihydroxy compound polyreaction, and described dihydroxy compound comprises polyether glycol and carboxylic dihydroxy compound, and end group activity-NCO adopts the low mass molecule alcohol sealing; Optical active group is to obtain by the open loop of side chain carboxyl, condensation reaction grafted ethene based compound, and the weight-average molecular weight of resin R is 4000-100000, acid number Av＜20mgKOH/g resin, iodine number Iv=20-100gI2/100g resin.
Described vulcabond is at least a in aromatic diisocyanate, aliphatic diisocyanate, the alicyclic diisocyanate.
Described vulcabond is preferably dicyclohexyl methane diisocyanate and hexamethylene diisocyanate and mixture, and the mass ratio of dicyclohexyl methane diisocyanate and hexamethylene diisocyanate is 100:1-1:100.
Described polyether glycol, its backbone structure contain at least HO-[CH2-CH (R)-O-] the n-OH segment, in the formula-R represents hydrogen atom or branched chain methyl, n is the 3-200 integer, the mass percentage content of polyether glycol in dihydroxy compound is 1-50%.
Described polyether glycol is preferably a kind of in triglycol, polytetramethylene glycol ethoxylated polyhydric alcohol, polytetrahydrofuran polyvalent alcohol, poly(propylene oxide) polyvalent alcohol, polybutylene oxide polyvalent alcohol or the polyoxypropyleneglycol, and the mass percentage content of polyether glycol in dihydroxy compound is preferably 10-30%.
The described carboxyl dihydroxy compound that contains is the two hydroxymethyl propionic acids of 2,2-or 3,5-resorcylic acid, and containing the mass percentage content of carboxyl dihydroxy compound in dihydroxy compound is 50-99%.
Described vinyl graft copolymer compound is 3,4-epoxycyclohexyl acrylate or glycidyl methacrylate or the combination of the two, and the vinyl graft copolymer compound is 0.8:1-1.5:1 with containing carboxyl dihydroxy compound mol ratio.
Described resin H obtains by vulcabond and terminal hydroxy group polydiene compound and at least a aryl oxide chainextender polyreaction, end group activity-NCO adopts the low mass molecule alcohol sealing, the resin weight-average molecular weight is 5000-200000, acid number Av=10-150mgKOH/g resin.
Described vulcabond is at least a in aromatic diisocyanate, aliphatic diisocyanate, the alicyclic diisocyanate.
Described vulcabond is preferably the cyclohexyl-methane vulcabond.
Described terminal hydroxy group diolefin contains repeating segment HO-[(CH2-CR=CH-CH2) y (CH2-CHCN) x] n-OH, wherein, R is hydrogen atom or branched chain methyl, x=0, y=1, n are the 1-200 positive integer.
Described terminal hydroxy group diolefin contains repeating segment HO-[(CH2-CR=CH-CH2) y (CH2-CHCN) x] n-OH, wherein, R is hydrogen atom or branched chain methyl, x=1, y=1-10, n are the 1-200 positive integer.
The method of synthetic above-mentioned R resin, elder generation's synthetic resins parent, resin matrix obtains by the hydrogen transference polyaddition reaction by vulcabond and side chain carboxyl dihydroxy compound and polyether glycol, end group activity-NCO adopts low mass molecule alcohol sealing end group, the side chain optical active group be by the epoxy monomer that contains unsaturated double-bond and side chain contain the carboxyl open loop, the condensation reaction grafting obtains.
The method of synthetic above-mentioned H resin is that vulcabond and terminal hydroxy group polydiene, the chainextender by rigid structure obtains by the hydrogen transference polyaddition reaction, and end group activity-NCO adopts the low mass molecule alcohol sealing.
Contain ultraviolet initiator in the caking agent of the present invention; the ultraviolet initiator that can add has benzophenone, rice to sneer ketone, 4-acetoxyl group-4 '-diethylamide benzophenone, Benzoin ethyl ether, Alpha-hydroxy isopropyl benzene ketone, Alpha-hydroxy phenylcyclohexane ketone, 2-phenyl-2; 2-dimethoxy acetyl benzophenone, 2-tertiary butyl anthraquinone, sec.-propyl thia anthraquinone, (morpholinyl benzoyl) 1-six bases 1; the 1(dimethylin) propane, benzil, bitter almond oil camphor etc., addition accounts for the 0.2-2% of solid amount.
Prepare caking agent solvent for use of the present invention and can be alcoholic solvent, ketones solvent, varsol, amide solvent, ether solvent, lipid solvent, the glycol kind solvent etc. of deriving, as methyl alcohol, ethanol, acetone, butanone, pimelinketone, N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide, methylene dichloride, benzene, toluene, ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether etc.The solid content of binding agent of the present invention is 0.5-20%.
Also can add uv-absorbing agent, backing dye, pigment, thermo-stabilizer in the caking agent, catch auxiliary agents such as oxygen agent.Addition accounts for the 0.2-5% of solid amount.
Owing to adopt technique scheme, the invention solves following technical problem:
1, caking agent adopts UV-curing technology, and caking agent is made up of R and two kinds of polyurethane acrylic resins of H and a small amount of ultraviolet initiator and auxiliary agent.The R resin be softening temperature and molecular weight lower contain polyether structure unit activity polyurethane acrylic resin, the H resin is the inertia polyurethane acrylic resin that the higher relatively main chain of molecular weight has polydiene and aryl oxide structure.
2, in order to solve a high oiliness bonding interface difficult problem, caking agent active ingredient R resin Composition main chain is introduced polyether segment, and inert component H component contains the similar segment of polydiolefin elastomerics.
3, in order to solve elastomerics, tack coat, matching problem between the base material, caking agent H resin Composition main chain is introduced the polydiene structural unit, and is all very good with snappiness and the consistency of block polydiene elastomerics and base material vinylidene chloride bottom.
4, solve unexposed initial bonding strength problem: caking agent does not contain monomer or oligopolymer, significantly improved softening temperature, design and elastomerics, base material has the analog structure polymer, caking agent is unexposed certain initial bonding strength, to guarantee problems such as being out of shape, come off does not appear in plate in cutting, examine processes such as version, packing, transportation.
5, printing process bonding force problem: caking agent contains a kind of R resin, its chain contains a kind of (methyl) acryloxy optical active group at least, produce superpower bonding force behind the ultraviolet light polymerization, can guarantee that elastomerics and base material can the strong shearing force when printing not be out of shape, peel off.
6, the high temperature resistant problem of caking agent: the adhesive resin main chain has designed polyethers and the high temperature resistant unit of special polydiene, and chainextender has also adopted the high temperature resistant unit of fragrant diether.
7, coating process problem: caking agent does not contain monomer or oligopolymer, dry back base material adhesion, and polyethers and polydiene soft chain segment snappiness are good, and the rolling of can high curvature after the base material coating curling is standby, and caking agent is low temperature resistant, high thermal resistance and later stage stability in storage are good.
8, combination resin technology: adjust inertia H resin content, can be combined into the different maximum exposure time, reduce the ultraviolet light polymerization internal stress and destroy, adapt to different sorts flexographic plate production needs.
The ultraviolet light polymerization caking agent of the present invention's preparation has the bonding force superpower to the high oiliness contact surface, and low temperature properties is good pliable and tough, has high temperature resistance and brokenization of ultraviolet ray ability, and easily coating is preserved, and satisfies the various performance needs of flexible resin version suitability for industrialized production fully.This caking agent does not contain the thickness performed polymer, and the softening temperature height can be applied on the base material in advance; The film snappiness is good, and the rolling of can high curvature after the base material coating curling is standby; Have the superpower bonding force of high oiliness elastomerics contact surface; Higher initial adhesion and permanent adhesion is arranged before the uv-exposure, do not have bubble between elastomerics and the base material when guarantee producing, cut indeformablely, do not come off; After the back of the body exposure of plate-making ultraviolet, can produce powerful bonding force, and snappiness is preferably arranged, guarantee that elastomerics and base material can the strong shearing force when printing not be out of shape, and peel off; Have better uvioresistant destructiveness, bonding force can not have decline along with the increase of exposure; Has the high temperature resistance destructiveness.
Embodiment
It is a kind of for the ultraviolet light polymerization caking agent of flexible resin version production and the synthetic method of main ingredient thing thereof that the present invention provides preparation.Concretely, caking agent adopts the polyurethane acrylate resin UV-curing technology, the main body of caking agent is polyurethane acrylic resin composition and a small amount of ultraviolet initiator and auxiliary agent, wherein a kind of R resin is that main chain contains the lower active polyurethane acrylic resin of polyether structure, softening temperature and molecular weight, its chain contains (methyl) acryloyl-oxy optical active group at least, its effect is to replace performed polymer, and the ultraviolet back of the body exposure when making a plate by the flexible resin version later stage makes it photocuring and produces superpower bonding force.Another kind of H resin backbone contains polydiene and fragrant two ether structures, the inertia polyurethane acrylic resin that molecular weight is higher relatively, and its effect is to provide high temperature resistant bonding force and good plate consistency for flexible plate.
Be of the present invention being described in detail below.
1, the R resin Composition among at first synthetic the present invention.
R resin Composition of the present invention is at first described.
Designed ultraviolet light polymerization component R resin in the caking agent, main chain contains polyether units, and its side chain contains (methyl) acryloyl-oxy optical active group.
The method of synthetic above-mentioned R resin, at first synthetic R resin matrix, the grafting active group reacts and adopts single stage method or two-step approach to finish then.
At first synthetic R resin matrix, R resin matrix are to obtain by the hydrogen transference polyaddition reaction by dihydroxy compound and polyether glycol that vulcabond and side chain contain carboxyl, and end group activity-NCO adopts the low mass molecule alcohol sealing.
The used vulcabond of synthetic R resin matrix of the present invention is detailed comprise 2,4 toluene diisocyanate (2,4--TDI), 2,6-tolylene diisocyanate (2,6-TDI) and their mixture, 4,4 '-diphenylmethanediisocyanate (MDI), 3,3 '-dimethyl 4,4 '-dicyclohexyl methane diisocyanate (DDI), 2,2,4-TMDI isophorone diisocyanate (IPDI), 4,4 '-dicyclohexyl methane diisocyanate (H12MDI), diformazan phenylene diisocyanate (XDI), tetramethyl xylene support vulcabond (TMXDI), 1,5-naphthalene diisocyanate (NDI), 1,6-hexylidene diisocyanate (1,6-HDI), 4,6-Xylene Diisocyanate (4,6-XDI), phenylene is to vulcabond (PPDI), 2,2,4-trimethylammonium-hexamethylene vulcabond (TMDI) etc.Owing to consider that caking agent film forming color and luster, bonding force and snappiness preferably adopt HMDI and HDI, the not flavescence of resin that the two combination is synthetic, the transparency height, snappiness is good, the mass ratio range HMDI/HDI=100/1-1/100 of HMDI/HDI, optimum scope is 90/10-70/30.
The synthetic used dihydroxy compound of R resin matrix of the present invention comprises polyether glycol and contains the carboxyl dihydroxy compound.
For oil-proofness and the tear strength that increases caking agent, R resin segment adds the polyether structure unit, and R resin of the present invention can add the polyether structure unit and comprise triglycol, polytetramethylene glycol ethoxylated polyhydric alcohol (PBD), polytetrahydrofuran polyvalent alcohol (PTMEG), poly(propylene oxide) polyvalent alcohol (PPO), polybutylene oxide polyvalent alcohol (PBO), polyoxypropyleneglycol (PPG) etc.Preferably add triglycol (TEG) or polyoxypropyleneglycol (PPG), for being 1-50%, optimum proportion is 10-30% in the dihydroxy compound mass percentage content for triglycol (TEG) or polyoxypropyleneglycol (PPG).
Synthetic R resin matrix of the present invention needs to add carboxylic dihydroxy compound, and carboxyl is the bridge of next step grafting active group, so containing the dihydroxy compound of carboxyl also is one of essential component, as the two hydroxymethyl propionic acids, 3 of 2,2-, 5-resorcylic acid etc.Preferably use DMPA, its molecular weight is less, has higher carboxyl contribution rate, and its still chainextender preferably, and it is 50-99% that the consumption of DMPA accounts for the dihydroxy compound mass percentage content, and optimum proportion is 70-90%.
In order to make the R resin have satisfactory stability, must seal R resin matrix end group activity-NCO, R resin matrix end group activity-NCO adopts low mass molecule alcohol, as butanols, ethanol, methyl alcohol sealing end group is preferably adopted in sealings such as methyl alcohol. and consumption is the 1%-20% of vulcabond mole number, and optimum proportion is 1%-10%.
The temperature of reaction of synthetic R resin matrix of the present invention is 40-140 ℃, is preferably in 50-100 ℃.
The catalyzer of the synthetic R resin matrix of the present invention of the synthetic the present invention of synthetic the present invention is all to can be used as the parent resin synthetic catalyst as fourth lead, stannous octoate, dibutyl tin laurate, N-methylmorpholine, piperazine, trialkyl phosphine, highly basic, basic salt, brill, iron, tertiary amine etc., dibutyl tin laurate preferably, consumption is the 0.01-10% of monomer of feeding intake, and optimum quantity is 0.1-5%.
The solvent of synthetic R resin matrix of the present invention must be selected for use and not contain the active hydrogen solvent of (comprising the water in the solvent), as the N that drying is crossed, and dinethylformamide, N,N-dimethylacetamide, toluene, methylethylketone, dioxane etc., or their mixture.The N of the most handy ammoniacum level, dinethylformamide (DMF) or N,N-dimethylacetamide (DMAC).
The reaction solid content of synthetic R resin matrix of the present invention is preferably in 20-70% at 10-80%.
The weight-average molecular weight of synthetic R resin matrix of the present invention is preferably 3000-50000 at 2000-100000, and acid number 20-200 mgKOH/g resin is preferably 50-150 mgKOH/g resin.
R resin side chain contain optical active group be by epoxy monomer and the side chain that contains the acryloyl-oxy unsaturated double-bond contain the carboxyl open loop, the condensation reaction grafting obtains.
The unsaturated epoxy monomer of R resin matrix grafting is preferably selected CMA (3,4-epoxycyclohexyl acrylate) or GMA (glycidyl methacrylate) or the combination of the two for use.Unsaturated epoxy monomer and carboxyl dihydroxy compound mol ratio are 0.8:1-1.5:1, are preferably 1:1-1.2:1.
The graft reaction temperature is 50-150 ℃, is preferably in 80-120 ℃.
R resin matrix grafting branch catalysts is mineral acid, alkali, amine, quaternary amine alkali, quaternary amine etc.
R resin matrix grafting branch reaction stopper has Resorcinol HQ, para benzoquinone PBQ, toluhydroquinone THQ, MEHQ HQMME, 2-Tert. Butyl Hydroquinone MTBHQ, 2,5 di tert butyl hydroquinone, nitroxyl free radical piperidines alcohol (ZJ-701) etc.Preferably adopt nitroxyl free radical piperidines alcohol (ZJ-701), its toxicity is less, and high temperature grafting polymerization inhibition effect is good, and by product is easily removed, and the surplus look of resin is less, does not influence caking agent later stage uv photopolymerization.
Synthetic R resin of the present invention preferably adopts following aftertreatment technology:
Solution cooling dilution after reaction is finished, the solvent of dilution has acetone, butanone, pimelinketone, pyrrolidone, N-Methyl pyrrolidone, ethyl acetate, tetrahydrofuran (THF), methyl alcohol, dioxane etc., the ratio of dilution should be controlled well, it is the control index with the solid content, the too low resin of solid content easily is emulsified in the water, influence the resin yield, solid content is too high, the easy conglomeration of resin, can not be dispersed into loose granular, synthetic R resin of the present invention preferably adopts dioxane as diluting solvent, and the ratio of dilution is solid content 1%-50%, and best ratio is 5%-30%.
Reaction solution after the dilution splashes in the deionized water separates out, preferably add small amounts of inorganic or organic acid in the deionized water, add the carboxyl that small amounts of inorganic or organic acid effect are the remaining salifies of reduction, also be beneficial to the stopper by product of removing high temperature oxidation, make resin property more stable.Available inorganic or organic acid has dilute sulphuric acid, phosphoric acid, dilute hydrochloric acid, Glacial acetic acid etc., preferably selects Glacial acetic acid for use, its corrodibility relatively a little less than, easy handling.
R resin washing back is dry, and temperature is controlled at 20 ℃-70 ℃, preferably control at 30-50 ℃, but vacuum-drying, air blast drying or natural room temperature drying.
Weight-average molecular weight (the GPC silica gel permeation chromatography of synthetic R resin of the present invention, polystyrene standard) at 4000-100000, best 8000-50000, acid number Av＜20mgKOH/g resin, best acid number Av＜3mgKOH/g resin,, iodine number Iv=20-100gI2/100g resin, preferably iodine number Iv=30-80I2/100g resin.
2, synthetic H resin Composition of the present invention.
H resin Composition of the present invention is at first described.
The H resin is that main chain contains the relative higher inertia polyurethane acrylic resin with fragrant ether structure ﹑ molecular weight of polydiene, its effect is to provide initial stage bonding force and good plate consistency for plate, and it has better uvioresistant destructiveness, and bonding force can not have downtrending along with the increase of exposure.
The method of synthetic above-mentioned H resin obtains by the hydrogen transference polyaddition reaction by vulcabond and terminal hydroxy group polydiolefin and chainextender, and end group activity-NCO adopts low mass molecule alcohol sealing end group.
The synthetic used vulcabond of H resin of the present invention can be selected the synthetic cited vulcabond of R resin for use.In order to guarantee that the H resin has higher molecular weight and softening temperature, vulcabond is preferably selected the vulcabond that contains rigid structure for use, as aromatic diisocyanate or hexa-atomic alicyclic diisocyanate, the best is selected transparent height for use, the dicyclohexyl methane diisocyanate of not flavescence (HMDI).
In order to make between caking agent and the Dan Ti ﹑ base material good matching is arranged, caking agent H resin Composition has been introduced the polydiene structural unit: HO-[(CH2-CR=CH-CH2) y (CH2-CHCN) x] n-OH is (wherein, R is hydrogen atom or branched chain methyl, y=1 when x=0, y=1-10 during x=1, n is the 1-200 positive integer), snappiness and the consistency of it and block polydiene elastomerics and base material vinylidene chloride bottom are all very good, and Dinging Xing of Re Wen ﹑ Kang You ﹑ tear strength is all effective.Synthetic H resin of the present invention is polybutadiene diol (HTPB) or polybutadiene-acrylonitrile copolymer glycol (HTBN) or the mixture of the two preferably.For being 1-80%, optimum proportion is 10-50% to the terminal hydroxy group polydiene in the dihydroxy compound mass percentage content.
In order to obtain higher molecular weight, synthetic H resin of the present invention is selected low molecule chainextender for use, chainextender should select for use the chain extension performance good, the dihydroxy compound high temperature resistant, that hardness is big, elasticity is high, at least a chainextender contains-O-(aryl)-O-structure, preferably selects DMPA and 1-hydroxyethyl-4-oxygen ethyl-hydroxyethyl benzene diether (liquid HQEE) or 1-hydroxyethyl-the two combination of 3-oxygen ethyl-hydroxyethyl benzene diether (liquid HER) for use.
The temperature of reaction of synthetic H resin of the present invention is 40-100 ℃, is preferably 60-80 ℃.
The catalyzer of synthetic H resin of the present invention such as fourth lead, stannous octoate, dibutyl tin laurate, trialkyl phosphine, highly basic, basic salt, brill, iron, tertiary amine etc. all can be used as the parent resin synthetic catalyst, dibutyl tin laurate preferably, consumption is the 0.01-10% of monomer of feeding intake, and optimum quantity is 0.1-5%.
The solvent of synthetic H resin of the present invention is selected for use and is not contained the active hydrogen solvent of (comprising the water in the solvent), as the N that drying is crossed, and dinethylformamide, N,N-dimethylacetamide etc., or their mixture.The N of the most handy ammoniacum level, dinethylformamide or N,N-dimethylacetamide.
Synthetic H resin of the present invention, solvent adopts branch to add, initial reaction stage preferably adopts mass polymerization or a small amount of solvent polymerization, to reduce the influence of solvent, promote molecular chain to increase, when molecular weight increases, stir and add solvent at need in batches, can obtain higher molecular weight like this, guarantee the initial bonding strength of caking agent.
The solid content of synthetic H resin of the present invention is preferably in 30-70% at 10-100%.
Synthetic H resin of the present invention, aftertreatment can be adopted the identical treatment process of R resin.
Synthesize the weight-average molecular weight of H resin of the present invention at 5000-200000, best 200000-100000, acid number Av=10-150mgKOH/g resin, preferably acid number Av=40-100mgKOH/g resin.
3, the preparation of caking agent and coating.
One of the characteristics of ultraviolet light polymerization caking agent of the present invention and advantage can be adjusted the performance of caking agent exactly flexibly according to the needs of flexographic plate elastomerics and different substrate materials performance.Owing to do not contain monomer or thickness performed polymer in the caking agent of the present invention, so the film shrinking percentage is minimum, many performances of caking agent such as initial bonding strength, curing bonding force, snappiness, shrinking percentage, high thermal resistance can make up to adjust by the ratio of R resin and H resin.
Contain photoinitiator in the caking agent of the present invention; the photosensitizers that can add has benzophenone, rice to sneer ketone, 4-acetoxyl group-4 '-diethylamide benzophenone, Benzoin ethyl ether, Alpha-hydroxy isopropyl benzene ketone, Alpha-hydroxy phenylcyclohexane ketone, 2-phenyl-2; 2-dimethoxy acetyl benzophenone, 2-tertiary butyl anthraquinone, sec.-propyl thia anthraquinone, (morpholinyl benzoyl) 1-six bases 1; the 1(dimethylin) propane, benzil, bitter almond oil camphor etc., addition accounts for more than 0.2% of solid amount.
Prepare caking agent solvent for use of the present invention and can be alcoholic solvent, ketones solvent, varsol, amide solvent, ether solvent, lipid solvent, the glycol kind solvent etc. of deriving, as methyl alcohol, ethanol, acetone, butanone, pimelinketone, N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide, methylene dichloride, benzene, toluene, ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether etc.
Also can add uv-absorbing agent, backing dye, pigment, thermo-stabilizer in the caking agent, catch auxiliary agents such as oxygen agent.
Caking agent amount of solid of the present invention accounts for more than 1% of quantity of solvent, be coated on the flexographic plate base materials such as polyethylene terephthalate (PET) through pretreated 80-150 μ m, polypropylene, triacetate the visible patent CN101144980 of processing mode.Coating method can adopt coating methods such as dip-coating, blade coating, extrusion coated.The general control of caking agent glue spread is at 1-5g/m2, thickness 0.1-5 μ m, and bottom and adhesive linkage total thickness are 0.2-10 μ m.But rolling is standby after being coated with the base material drying of caking agent, lucifuge room temperature preservation 18 months, and quality is no change almost.
Caking agent of the present invention, has good bonding effect to containing high oil mass elastomerics contact surface, naphthenic oil, fourth oil, the contour oils contact surface of silicone oil are all shown good bonding force, when the elastomer layer oleaginousness〉20%, initial bonding strength is not less than 10g/cm, the exposure bonding force〉1000/cm.
Be synthetic and preparation example of the present invention below, can illustrate in greater detail ultraviolet light polymerization caking agent of the present invention, but the present invention be not limited to following example.
Synthetic example 1 (synthetic R resin: R-1 ﹟)
In taking back the four-hole boiling flask of stream device and drying tube, 500 ml add the DMF (N that 90 ml cross through anhydrous sodium sulfate drying, dinethylformamide) and 70.83g (0.27mol) HMDI (dicyclohexyl methane diisocyanate), 11.77g (0.07mol) HDI (hexamethylene diisocyanate), stir evenly the back and add TEG (triglycol) 12.01g(0.08mol), DMPA (2, the two hydroxymethyl propionic acids of 2-) 34.87g(0.26mol), after treating dissolving fully, add dibutyl tin laurate 0.5g, temperature is 60 ℃ in being warming up to, after the insulation reaction 2 hours, add DMF110ml, continue reaction, 5.5 add dibutyl tin laurate 0.1g after hour, end-block agent methyl alcohol 3.20g (0.10mol), after half an hour, synthetic parent resin RM reaction is finished.
In above-mentioned parent resin RM reaction solution, add DMF160 ml, BTMA (benzyl trimethyl ammonium chloride) 5.60g, TPP (triphenylphosphine) 2.1g, ZJ-701 (nitroxyl free radical piperidines alcohol) 1.4g, CMA (3 successively, 4-epoxycyclohexyl acrylate) 56.48 g (0.31mol), stir, 90 ℃ were reacted 2 hours, be warmed up to 120 ℃ then and continue reaction end in 2 hours, be cooled to room temperature, the RM graft reaction is finished.
In cooled reaction solution, add the DOX(dioxane) dilution, reaction solution after the dilution is splashed into to contain in the 90ml Glacial acetic acid 25L deionized water and separates out solid resin, solid resin washs back 50 ℃ of following vacuum-dryings and gets white solid thing R-1 ﹟, GPC weight-average molecular weight Mw=17900, acid number Av＜3mgKOH/g resin, iodine number Iv=37.32gI2/100g resin.
Synthetic example 2 (synthetic R resin: R-2 ﹟)
In taking back the four-hole boiling flask of stream device and drying tube, 500 ml add the DMF (N that 90 ml cross through anhydrous sodium sulfate drying, dinethylformamide) and 70.83g (0.27mol) HMDI (dicyclohexyl methane diisocyanate), 11.77g (0.07mol) HDI (hexamethylene diisocyanate), stir evenly the back and add TEG (triglycol) 12.01g(0.08mol), DMPA (2, the two hydroxymethyl propionic acids of 2-) 34.87g(0.26mol), after treating dissolving fully, add dibutyl tin laurate 0.5g, temperature is 60 ℃ in being warming up to, after the insulation reaction 2 hours, add DMF110ml, continue reaction, 5.5 add dibutyl tin laurate 0.1g after hour, end-block agent methyl alcohol 3.20g (0.10mol), after half an hour, synthetic parent resin RM reaction is finished.
In above-mentioned parent resin RM reaction solution, add DMF160 ml, BTMA (benzyl trimethyl ammonium chloride) 5.60g, TPP (triphenylphosphine) 2.1g, ZJ-701 (nitroxyl free radical piperidines alcohol) 1.4g, GMA (glycidyl methacrylate) 42.65g (0.30mol) successively, stir, 90 ℃ were reacted 2 hours, be warmed up to 120 ℃ then and continue reaction end in 2 hours, be cooled to room temperature, the RM graft reaction is finished.
Aftertreatment technology is with example 1, R-2 ﹟ resin GPC weight-average molecular weight Mw=17500, acid number Av＜3mgKOH/g resin, iodine number Iv=39.65gI2/100g resin.
Synthetic example 3 (synthetic R resin: R-3 ﹟)
In taking back the four-hole boiling flask of stream device and drying tube, 500 ml add 81.33g (0.31mol) HMDI (dicyclohexyl methane diisocyanate), 6.73g (0.04mol) HDI (hexamethylene diisocyanate), stir evenly the back and add the PPG-1000 (polyoxypropyleneglycol that dewaters through decompression, molecular weight 1000 ± 70, hydroxyl value 105-117)) 10g(0.01mol) stir after, add dibutyl tin laurate 0.5g, temperature is 80 ℃ in being warming up to, behind the bulk reaction 1.5 hours, be cooled to 60 ℃, add the DMF (N that 90 ml cross through anhydrous sodium sulfate drying, dinethylformamide), DMPA (2, the two hydroxymethyl propionic acids of 2-) 45.60g(0.34mol), react and add DMF110ml after one hour, continue reaction and add dibutyl tin laurate 0.1g, end-block agent methyl alcohol 3.20g (0.10mol) after 4 hours, after half an hour, synthetic parent resin RM reaction is finished.
In above-mentioned parent resin RM reaction solution, add DMF160 ml, BTMA (benzyl trimethyl ammonium chloride) 7.11g, TPP (triphenylphosphine) 2.1g, 4.28 (nitroxyl free radical piperidines alcohol) 1.4g, CMA (3 successively, 4-epoxycyclohexyl acrylate) 71.24g (0.39mol), stir, 90 ℃ were reacted 2 hours, be warmed up to 120 ℃ then and continue reaction end in 2 hours, be cooled to room temperature, the RM graft reaction is finished.
Aftertreatment technology is with example 1, R-3 ﹟ resin GPC weight-average molecular weight Mw=21400, acid number Av＜3mgKOH/g resin, iodine number Iv=41.20gI2/100g resin.
Synthetic example 4 (synthetic R resin: R-4 ﹟)
Take back the PPG-1000 (polyoxypropyleneglycol that adds 91.82g (0.35mol) HMDI (dicyclohexyl methane diisocyanate) and dewater through decompression in the four-hole boiling flask of stream device and drying tube at 500 ml, molecular weight 1000 ± 70, hydroxyl value 105-117)) 10g(0.01mol) stir after, add dibutyl tin laurate 0.5g, temperature is 80 ℃ in being warming up to, behind the bulk reaction 1.5 hours, add the DMF (N that 90 ml cross through anhydrous sodium sulfate drying, dinethylformamide), DMPA (the two hydroxymethyl propionic acids of 2,2-) 45.60g(0.34mol), react and add DMF110ml after one hour, continue reaction after 4 hours, be cooled to 60 ℃, add dibutyl tin laurate 0.1g, end-block agent methyl alcohol 3.20g (0.10mol), after half an hour, synthetic parent resin RM reaction is finished.
In above-mentioned parent resin RM reaction solution, add DMF160 ml, BTMA (benzyl trimethyl ammonium chloride) 7.11g, TPP (triphenylphosphine) 2.1g, 4.28 (nitroxyl free radical piperidines alcohol) 1.4g, GMA (glycidyl methacrylate) 55.58g (0.391mol) successively, stir, 90 ℃ were reacted 2 hours, be warmed up to 120 ℃ then and continue reaction end in 2 hours, be cooled to room temperature, the RM graft reaction is finished.
Aftertreatment technology is with example 1, R-4 ﹟ resin GPC weight-average molecular weight Mw=21400, acid number Av＜3mgKOH/g resin, iodine number Iv=44.08gI2/100g resin.
Synthetic example 5 (synthetic H resin: H-1 ﹟)
In taking back the four-hole boiling flask of stream device and drying tube, 1000 ml add 131.18g (0.50mol) HMDI (dicyclohexyl methane diisocyanate), 50g (about 0.05mol) HDPB (polybutadiene diol, Mn:2000, hydroxyl value: about 1.00m mol/g), dibutyl tin laurate 0.5g, temperature is 80 ℃ in being warming up to after stirring, behind the bulk reaction 1 hour, add 110mlDMAC (N, the N-N,N-DIMETHYLACETAMIDE), DMPA (2, the two hydroxymethyl propionic acids of 2-) 53.65g(0.40mol), HQEE-L (4-hydroxyethyl oxygen ethyl-1-hydroxyethylbenzene diether) 12.11g (0.05mol), continue reaction, 50mlDMAC (N was added in every reaction in 0.5 hour, the N-N,N-DIMETHYLACETAMIDE), amount to 250ml 5 times, total reaction time adds dibutyl tin laurate 0.1g after 5.5 hours, end-block agent methyl alcohol 3.20g (0.10mol), after half an hour, synthetic H resin reaction is finished.
Aftertreatment technology is with example 1, H-1 ﹟ resin GPC weight-average molecular weight Mw=47840, acid number Av=90.87mgKOH/g resin.
Synthetic example 6 (synthetic H resin: H-2 ﹟)
In taking back the four-hole boiling flask of stream device and drying tube, 1000 ml add 104.94g (0.40mol) HMDI (dicyclohexyl methane diisocyanate), 16.82g (0.10mol) HDI (hexamethylene diisocyanate), 40g (about 0.04mol) HDPB (polybutadiene diol, Mn:2000, hydroxyl value: about 1.00m mol/g), dibutyl tin laurate 0.5g, temperature is 80 ℃ in being warming up to after stirring, behind the bulk reaction 1 hour, add 110mlDMAC (N, the N-N,N-DIMETHYLACETAMIDE), DMPA (2, the two hydroxymethyl propionic acids of 2-) 40.24g(0.30mol), HER-L (1-hydroxyethyl-3-oxygen ethyl-hydroxyethyl benzene diether) 38.76g (0.16mol), continue reaction, 50mlDMAC (N was added in every reaction in 0.5 hour, the N-N,N-DIMETHYLACETAMIDE), amount to 250ml 5 times, total reaction time adds dibutyl tin laurate 0.1g after 5.5 hours, end-block agent methyl alcohol 3.20g (0.10mol), after half an hour, synthetic H resin reaction is finished.
Aftertreatment technology is with example 1, H-2 ﹟ resin GPC weight-average molecular weight Mw=45360, acid number Av=69.90mgKOH/g resin.
Synthetic example 7 (synthetic H resin: H-3 ﹟)
In taking back the four-hole boiling flask of stream device and drying tube, 1000 ml add 131.18g (0.50mol) HMDI (dicyclohexyl methane diisocyanate), 50g (about 0.025mol) HTBN (hydroxy-terminated polybutadienes vinyl cyanide, Mn:2000, hydroxyl value: about 0.50m mol/g), dibutyl tin laurate 0.5g, temperature is 80 ℃ in being warming up to after stirring, behind the bulk reaction 1 hour, add 110mlDMAC (N, the N-N,N-DIMETHYLACETAMIDE), DMPA (2, the two hydroxymethyl propionic acids of 2-) 53.65g(0.40mol), HQEE-L (4-hydroxyethyl oxygen ethyl-1-hydroxyethylbenzene diether) 18.17g (0.075mol), continue reaction, 50mlDMAC (N was added in every reaction in 0.5 hour, the N-N,N-DIMETHYLACETAMIDE), amount to 250ml 5 times, total reaction time adds dibutyl tin laurate 0.1g after 5.5 hours, end-block agent methyl alcohol 3.20g (0.10mol), after half an hour, synthetic H resin reaction is finished.
In cooled reaction solution, add the DOX(dioxane) dilution, reaction solution after the dilution is splashed into to contain in the 90ml Glacial acetic acid 25L deionized water and separates out solid resin, solid resin washs back 50 ℃ of following vacuum-dryings and gets white solid thing H-3 ﹟ resin GPC weight-average molecular weight Mw=51790, acid number Av=88.70mgKOH/g resin.
Synthetic example 8 (synthetic H resin: H-4 ﹟)
In taking back the four-hole boiling flask of stream device and drying tube, 1000 ml add 104.94g (0.40mol) HMDI (dicyclohexyl methane diisocyanate), 16.82g (0.10mol) HDI (hexamethylene diisocyanate), 40g (about 0.02mol) HTBN (hydroxy-terminated polybutadienes vinyl cyanide, Mn:2000, hydroxyl value: about 0.50m mol/g), dibutyl tin laurate 0.5g, temperature is 80 ℃ in being warming up to after stirring, behind the bulk reaction 1 hour, add 110mlDMAC (N, the N-N,N-DIMETHYLACETAMIDE), DMPA (2, the two hydroxymethyl propionic acids of 2-) 40.24g(0.30mol), HER-L (1-hydroxyethyl-3-oxygen ethyl-hydroxyethyl benzene diether) 43.61g (0.16mol), continue reaction, 50mlDMAC (N was added in every reaction in 0.5 hour, the N-N,N-DIMETHYLACETAMIDE), amount to 250ml 5 times, total reaction time adds dibutyl tin laurate 0.1g after 5.5 hours, end-block agent methyl alcohol 3.20g (0.10mol), after half an hour, synthetic H resin reaction is finished.
Aftertreatment technology is with example 1, H-4 ﹟ resin GPC weight-average molecular weight Mw=50760, acid number Av=68.85mgKOH/g resin.
Select above-mentioned synthetic R-1 ﹟ resin and H-1 ﹟ resin for use, preparation embodiment caking agent N-1 ﹟.
Caking agent N-1 ﹟: ethylene glycol monoemethyl ether 100g, toluene 50g, R-1 ﹟ 10g, H-1 ﹟ 10g, dissolved solution.Add initiator (184) 0.5g, 2 then, 6-d-tert-butyl-p-cresol 0.2g, Fc-4430#(3M company produce) 0.1g, under yellow safety lamp, in encloses container, stirred 1 hour, obtain caking agent 1 ﹟.
According to following table 1 ratio and caking agent N-1 ﹟ blending process (solvent, initiator, auxiliary agent ratio are identical) preparation caking agent N-2 ﹟ to N-15 ﹟.
The speed of a motor vehicle of above-mentioned caking agent with 25m/min is coated on the underlying membrane, and 50 ℃ were descended dry 15 minutes, and glue spread is 1g/ square metre, and thickness is 1 μ m.Be 3.94mm or 1.70mm flexographic plate photosensitive resin layer with being coated with the thickness that the support of caking agent and E.I.Du Pont Company or Lekai group produce, at 120 ℃, under the pressure 0.15-14MPa high temperature compound flexible photosensitive resin plate.The Jiangsu flexible platemaking machine 365nm of safe instrument group UV-light light intensity is 7.3 milliwatt/square centimeters, and the BLD-200S electron detachment trier that peeling force uses Labthink Instruments Co., Ltd. to produce is measured.Wherein, F0 is unexposed bonding force, and F1 is 1 minute bonding force of ultraviolet back of the body exposure, and F20 is the ultraviolet 20 fens bonding forces that just exposing, and bonding force unit is g/cm.
Table 1
Annotate: the PU-II is urethane resin in the comparative example, and PA-1 is active polyacrylic resin, and PT-B is the solvent-based thermal cladding resin, is Lekai film company and produces, and MPODA is reactive monomer 2-methyl isophthalic acid, 3 one propylene glycol diacrylates.
As can be seen from the above table:
1. embodiments of the invention N-1 ﹟ does not contain the pre-polymerization monomer to N-6 ﹟ caking agent, film is tack-free, can realize precoating, good stability (the anti-120 ℃ of high temperature of 18 months quality guaranteed perioves of pre-coating film) ﹔ caking agent, to the 10g/cm of high oiliness elastomerics initial bonding strength greater than the flexographic plate production requirement, can produce powerful bonding force behind 1 minute uv-exposure, it is pliable and tough that bonding force is higher than 20 minutes uv-exposure caudacorias of 1000g/cm standard ﹔ far away, shrink little, plate is indeformable, and bonding force satisfies plate Yaos Qiu ﹔ in addition, from N-5 ﹟-N-12 ﹟ embodiment as can be seen, by adjusting R resin and H resin ratio, can alleviate ultraviolet overexposure internal stress and destroy, the uv-exposure bonding force descended seldom in 20 minutes, can be used for the production of the demanding 1.70mm flexographic plate of uvioresistant overexposure destructiveness.
2. N-13 ﹟, N-14 ﹟ caking agent contain the pre-polymerization monomer in the comparative example, film glues hand, can not realize precoating, non-refractory, poor stability, the uv-exposure caudacoria shrinks, internal stress is big, and is all very little to high oiliness interface initial bonding strength and ultraviolet light polymerization bonding force, do not reach flexographic plate Sheng and produces that to Yao Qiu ﹔ N-15 ﹟ hot melt adhesive film crisp, bonding force does not reach standard, can not use.
Claims (6)
1. ultraviolet light polymerization caking agent, mainly by resin body, solvent, ultraviolet initiator and auxiliary agent are formed, it is characterized in that: its resin body is formed by containing the inertia polyurethane acrylic resin H that polyether structure active polyurethane acrylic resin R and main chain have polydiene and aryl oxide structure, the weight ratio of resin R and resin H is 1:10-10:1 in the caking agent, the resin matrix of described resin R obtains by vulcabond and dihydroxy compound polyreaction, described dihydroxy compound comprises polyether glycol and carboxylic dihydroxy compound, and end group activity-NCO adopts the low mass molecule alcohol sealing; Optical active group is to obtain by the open loop of side chain carboxyl, condensation reaction grafted ethene based compound, and the weight-average molecular weight of resin R is 4000-100000, acid number Av＜20mgKOH/g resin, iodine number Iv=20-100gI
2/ 100g resin;
Described grafted ethene based compound is 3,4-epoxycyclohexyl acrylate or glycidyl methacrylate or the combination of the two, and the vinyl graft copolymer compound is 0.8:1-1.5:1 with containing carboxyl dihydroxy compound mol ratio;
Described resin H obtains by vulcabond and terminal hydroxy group polydiene compound and at least a aryl oxide chainextender polyreaction, end group activity-NCO adopts the low mass molecule alcohol sealing, the resin weight-average molecular weight is 5000-200000, acid number Av=10-150mgKOH/g resin.
2. ultraviolet light polymerization caking agent according to claim 1 is characterized in that: described vulcabond is at least a in aliphatic diisocyanate, the alicyclic diisocyanate.
3. ultraviolet light polymerization caking agent according to claim 1, it is characterized in that: described polyether glycol, its backbone structure contains HO-[CH at least
2-CH (R)-O-]
n-OH segment, in the formula-R represents hydrogen atom or branched chain methyl, and n is the 3-200 integer, and the mass percentage content of polyether glycol in dihydroxy compound is 1-50%.
4. ultraviolet light polymerization caking agent according to claim 1, it is characterized in that: the described carboxyl dihydroxy compound that contains is 2, the two hydroxymethyl propionic acids of 2-or 3,5-resorcylic acid, containing the mass percentage content of carboxyl dihydroxy compound in dihydroxy compound is 50-99%.
5. ultraviolet light polymerization caking agent according to claim 1, it is characterized in that: described terminal hydroxy group diolefin contains repeating segment HO-[(CH
2-CR=CH-CH
2)
y(CH
2-CHCN)
x]
n-OH, wherein, R is hydrogen atom or branched chain methyl, x=0, y=1, n are the 1-200 positive integer.
6. ultraviolet light polymerization caking agent according to claim 1, it is characterized in that: described terminal hydroxy group diolefin contains repeating segment HO-[(CH
2-CR=CH-CH
2)
y(CH
2-CHCN)
x]
n-OH, wherein, R is hydrogen atom or branched chain methyl, x=1, y=1-10, n are the 1-200 positive integer.
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| CN105238280A (en) * | 2011-12-08 | 2016-01-13 | 日本化药株式会社 | Optical member, ultraviolet curable resin composition, and cured product |
| CN103698979B (en) * | 2012-09-28 | 2017-04-12 | 乐凯华光印刷科技有限公司 | Water-washable flexible resin plate and making method thereof |
| CN104723716A (en) * | 2013-12-19 | 2015-06-24 | 乐凯华光印刷科技有限公司 | Directly laser-made metal-based resin plate and method for making same |
| CN103770486B (en) * | 2013-12-30 | 2017-01-04 | 深圳市柏星龙创意包装股份有限公司 | Cold foil technology and the UV glue for this technique |
| CN105774287B (en) * | 2014-12-18 | 2019-01-15 | 乐凯华光印刷科技有限公司 | A kind of flexographic plate heat cure Metal Substrate support and preparation method thereof |
| JP6512133B2 (en) * | 2016-02-25 | 2019-05-15 | 株式会社オートネットワーク技術研究所 | Wire protection member, method for manufacturing the same, and wire harness |
| CN107417905B (en) * | 2017-05-11 | 2019-11-26 | 清华大学深圳研究生院 | A kind of unsaturated polyether, light-cured resin and preparation method thereof |
| CN108129587B (en) * | 2017-12-29 | 2020-06-23 | 广州五行材料科技有限公司 | High-adhesion resin and preparation method and application thereof |
| CN108841316B (en) * | 2018-06-22 | 2021-11-19 | 南昌航空大学 | Preparation method of ultraviolet-cured terbium-bonded high polymer material |
| KR102323585B1 (en) * | 2018-09-03 | 2021-11-05 | 아라까와 가가꾸 고교 가부시끼가이샤 | Active energy ray-curable adhesive composition, cured product and adhesive sheet |
| KR20200086399A (en) * | 2019-01-08 | 2020-07-17 | 현대모비스 주식회사 | A composition for automobile interior skin, manufacturing method thereof, and automobile interior skin manufactured using the same |
| EP3839624B1 (en) * | 2019-12-18 | 2023-09-13 | Nivarox-FAR S.A. | Method for manufacturing a timepiece component |
| CN111534269B (en) * | 2020-05-07 | 2022-04-12 | 苏州金枪新材料股份有限公司 | Two-component flexible acrylate structural adhesive for bonding liquid crystal screen and preparation method thereof |
| CN113999644A (en) * | 2021-11-24 | 2022-02-01 | 浙江科力厌氧胶有限公司 | UV adhesive and preparation method thereof |
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