CN104203992B - Poly-(methyl) acrylate and manufacture method, monomer composition, solidfied material and printed circuit board (PCB) - Google Patents

Poly-(methyl) acrylate and manufacture method, monomer composition, solidfied material and printed circuit board (PCB) Download PDF

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CN104203992B
CN104203992B CN201380017235.5A CN201380017235A CN104203992B CN 104203992 B CN104203992 B CN 104203992B CN 201380017235 A CN201380017235 A CN 201380017235A CN 104203992 B CN104203992 B CN 104203992B
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methyl
acrylate
monomer
monomer composition
acryloyl group
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CN104203992A (en
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崔城豪
志村优之
依田健志
宇敷滋
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Taiyo Holdings Co Ltd
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Taiyo Holdings Co Ltd
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/22Secondary treatment of printed circuits
    • H05K3/28Applying non-metallic protective coatings
    • H05K3/285Permanent coating compositions
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/22Secondary treatment of printed circuits
    • H05K3/28Applying non-metallic protective coatings
    • H05K3/285Permanent coating compositions
    • H05K3/287Photosensitive compositions

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention provides the manufacture method that can be obtained excellent poly-(methyl) acrylate of the physical characteristics such as adaptation, hardness, chemical proofing, heat resistance and insulating properties by quickly reaction.Obtain the manufacture method of a kind of poly-(methyl) acrylate; it is characterized in that; the monomer composition obtained adding the compound with NCO in the monomer with (methyl) acryloyl group heats, so that the monomer with (methyl) acryloyl group is polymerized at 140 DEG C to 170 DEG C.

Description

Poly-(methyl) acrylate and manufacture method, monomer composition, solidfied material and printed circuit board (PCB)
Technical field
The present invention relates to the manufacture method of poly-(methyl) acrylate, particularly relate to by isocyanic acid The monomer with (methyl) acryloyl group is made to occur polymerization to obtain poly-(methyl) propylene in the presence of ester The manufacture method of acid esters.
And then, poly-(methyl) acrylate of the present invention relates to be obtained by above-mentioned manufacture method, comprise Its solidification compound, its solidfied material and comprise its printed circuit board (PCB).
Background technology
Poly-(methyl) acrylate (acrylic resin) has high transparent/resistance to impact, It is prone to thermoplastic shaping/coloring, therefore except being used for building, the vehicles as the substitute of unorganic glass Window materials etc. outside, also fit as the parts of electric/electronic, commodity, office appliance etc. For multiple use.
Acrylic resin can utilize irradiation ultraviolet radiation or electricity by adding in (methyl) acrylate Son bundle isoreactivity energy-ray and produce the free-radical generating agent of free radical and carry out radical polymerization (crosslinking is anti- Should) manufacture.Alternatively, it is also possible to by adding peroxide in (methyl) acrylate and heating And the incompatible manufacture of radical polymerization poly-(methyl) acrylate carried out.
As these object lesson, such as, Patent Document 1 discloses and comprise (methyl) acrylate Ultraviolet-curing resin composition with Photoepolymerizationinitiater initiater.Patent document 1 is recorded by with height Pressure mercury lamp makes the technological thought that resin solidifies to resin combination irradiation ultraviolet radiation.
And then, patent document 2 is recorded by hindered amine compound and the existence of organic peroxide The free radical type adhesive composition that lower utilization heating makes (methyl) acrylate carry out solidifying and obtains, makes (methyl) acrylate below 150 DEG C in a low temperature of solidify.
Additionally, in patent document 3 record, about comprise there is hydroxyl (methyl) acrylate, Blocked isocyanate, the blend of Photoepolymerizationinitiater initiater, carry out photocuring and heat cure afterwards Method.
Prior art literature
Patent document
Patent document 1: Japanese Laid-Open Patent Publication 61-31449
Patent document 2: Japanese Unexamined Patent Publication 2008-94913
Patent document 3:2004-513197
Summary of the invention
The problem that invention is to be solved
But, according to patent document 1, utilize optical free radical producing agent to be polymerized, thus react speed Degree can rise, but curing degree is low.The solidfied material being affected by obtaining may not obtain sufficient adaptation, resistance to Chemicals.
It addition, the manufacture of the acrylate of patent document 2 employs peroxide.Peroxide is danger Danger product, the most disposable.
Even if it addition, acrylate also can occur autohemagglutination (homopolymerization) to react by merely heating, but because of Heat is relatively stablized and is needed to be heated to about more than 200 DEG C by acryloyl group.In this case, not only at energy There is the leeway of research in efficiency aspect, and as the base material of the object using the composition containing acrylate Heat resistance also become problem.
And then, in patent document 3, (methyl) acrylate is used as a composition in polymerization, it is necessary to There is hydroxyl.That is, the hydroxyl of (methyl) acrylate is preferentially carried out with the reaction of isocyanates, and not The homopolymerization of (methyl) acrylate can occur.
It should be noted that as disclosed in patent document 3, it is known that isocyanates is for manufacturing amino The raw material of formic acid esters, urea derivative etc., it easily reacts with hydroxyl, amine, phenol, mercaptan etc., But apply, entirely without report in reacting about the manufacture at poly-(methyl) acrylate.
While it is true, it is an object of the invention to, it is provided that can by quickly reaction obtain adaptation, Poly-(methyl) propylene that the physical characteristics such as hardness, chemical proofing, heat resistance and insulating properties are excellent The manufacture method of acid esters.
And then, it is an object of the invention to, it is provided that the manufacture method of poly-(methyl) acrylate is used Monomer composition, its solidfied material and comprise its printed circuit board (PCB).
For solving the scheme of problem
In order to solve above-mentioned purpose, the feature of the manufacture method of poly-(methyl) acrylate of the present invention exists In, by adding in the monomer with (methyl) acryloyl group, there is the compound of NCO and obtain To monomer composition heat at 140 DEG C to 170 DEG C, so that having (methyl) acryloyl group Monomer be polymerized.
By the method, adaptation, hardness, chemical proofing, heat resistance and insulation can be produced Property etc. excellent poly-(methyl) acrylate such as physical characteristic.
And then, in accordance with the invention it is possible to obtain a kind of monomer composition, it is characterised in that comprise made Poly-(methyl) acrylate made.
This monomer composition is owing to without the functional group reacted at normal temperatures, therefore storage stability is excellent Different.
The monomer composition of the present invention can by heat cure, photocuring or both and be made into closely sealed Property, solidfied material (poly-(methyl) acrylic acid that the physical characteristic such as chemical proofing and heat resistance is excellent Ester), therefore, it is possible to be used as ink or the covering of printed circuit board (PCB) of such as printed circuit board (PCB) printing.
The effect of invention
Manufacturing method according to the invention, it is possible to make that in the presence of isocyanates there is (methyl) propylene The monomer of acyl group at a lower temperature, carry out homopolymerization in the short time, it is possible to obtain adaptation, hardness, Poly-(methyl) acrylate that the physical characteristics such as chemical proofing, heat resistance and insulating properties are excellent Solidfied material or film.
And then, the most there is not polymerisation in the monomer composition of the present invention, therefore, it is possible to a liquid The form stable ground of type preserves.By monomer composition being coated printed circuit board (PCB) and making it solidify, from And make the physical characteristic excellences such as adaptation, hardness, chemical proofing, heat resistance and insulating properties Insulating material for printed circuit board, if adding coloring pigment etc., then can be used for as ink composite The printing purposes of printed circuit board (PCB).
Accompanying drawing explanation
Fig. 1 is the differential scanning calorimetric curve of the monomer composition illustrating the present invention and the material for comparing Figure.
Fig. 2 is to illustrate the infrared spectrophotometer when monomer composition of the present invention is heated to different temperatures The figure of the change of middle absorbance.
Detailed description of the invention
In the present invention, will have the monomer (also referred to as (methyl) acrylate) of (methyl) acryloyl group With the mixture of isocyanates as monomer composition, by it is entered with the stipulated time at the specified temperature Row heating, so that the monomer with (methyl) acryloyl group carries out homopolymerization, thus prepares poly-(methyl) Acrylate.
It addition, the homopolymerization of (methyl) acrylate is generally occurred by the heating of more than 200 DEG C, and this Invention monomer composition by by it at 140 DEG C~170 DEG C, at preferably 150 DEG C~170 DEG C heat 15 Second~1000 seconds and make (methyl) acrylate contained therein be polymerized.During less than 140 DEG C, (first Base) polymerization of acrylate becomes insufficient, and during higher than 170 DEG C, have and execute as monomer composition The substrate giving object produces the dysgenic possibility of calorifics.By at the temperature model of 140 DEG C~170 DEG C Carrying out 15 seconds~the heating of 1000 seconds in enclosing, the almost all double bond in (methyl) acryloyl group is opened, and becomes For having the state that the monomer of (methyl) acryloyl group is cross-linked.
Reaction of formation about poly-(methyl) acrylate in the present invention, it is believed that: if at isocyanide Heat under the state that acid esters and (methyl) acrylate coexist, then the existence of (methyl) acryloyl group promotees Enter the trimerizing reaction of isocyanates, and the trimerizing of isocyanates reacts, and can produce raising (methyl) The such result of activity of acryloyl group.
It addition, present invention it is preferred that, having that the monomer of (methyl) acryloyl group do not has can The functional group reacted with isocyanates.Generally, isocyanates with there is OH, NH2Have Deng to isocyanates The compound reaction of the hydrogen atom of activity, but not with (methyl) acryloyl group of (methyl) acrylate React.Therefore, when making (methyl) acrylate react with isocyanates, active hydrogen is used (methyl) acrylate such as (methyl) acrylate of atom.
But, in order to make the polymerization of (methyl) acrylate preferentially carry out, the method for the present invention or monomer In composition, and then as other composition, it is also preferred that have can react with isocyanates without any The compound of functional group.
Furthermore it is possible to think that the heat produced partly by the trimerization reaction of isocyanates also contributes to The carrying out of (methyl) acrylic ester polymerization.
The film utilizing the product that obtained by the reaction mechanism of the present invention and obtain have high adhesion, The physical characteristic that chemical proofing, heat resistance etc. are the most excellent, therefore extremely can have in multiple use Effect ground uses.
It addition, in the trimerization of isocyanates, form the isocyanuric acid ester with triazine ring structure.By comprising Film that the compound of triazine ring structure is constituted or the heat resistance of solidfied material and insulating properties are excellent, therefore conduct Heat proof material, insulating materials are useful.
It addition, during more than use trifunctional isocyanates, the network knot with triazine skeleton also can be formed Structure.Have the material of this network structure have the film improved containing this material or the heat resistance of solidfied material, The effect of chemical proofing etc..
As it has been described above, the method according to the invention, generate and comprise poly-(methyl) acrylate and isocyanic acid The reactant mixture of the oligomer such as the tripolymer of ester, this reactant mixture solidifies, thus constitutes closely sealed Property, film that hardness, chemical proofing, heat resistance and insulating properties are excellent.
[there is the monomer of (methyl) acryloyl group]
The monomer in the present invention, with (methyl) acryloyl group has the (first of more than 1 in 1 molecule Base) acryloyl group.Can be with isocyanic acid it addition, preferably do not have containing (methyl) acryl monomer The compound of the functional group of ester reaction.
Herein, it is possible to the functional group reacted with isocyanates refers to the functional group of active hydrogen atom, example As OH base, NH base, NH can be enumerated2Base, SH base and COOH base.The tool used in the present invention The monomer having (methyl) acryloyl group does not the most have these functional groups.
(methyl) acrylate used in the present invention such as can enumerate (methyl) acrylic acid 2-(2- Ethoxy ethoxy) ethyl ester, (methyl) butyl acrylate, (methyl) stearyl acrylate ester, (methyl) Tridecyl acrylate, (methyl) lauryl acrylate, (methyl) isobornyl acrylate, (first Base) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-benzene oxygen Simple function (methyl) acrylate such as base ethyl ester, and multifunctional (methyl) acrylate compounds, Described multifunctional (methyl) acrylate compounds comprises: 1,3 butylene glycol two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, diethylene glycol Two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) Acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, neopentylglycol diacrylate etc. two Sense (methyl) acrylic acid;The trifunctionals such as trimethylolpropane trimethacrylate (methyl) acrylic acid; And two trimethylolpropane tetra-acrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol 6 third (methyl) acrylate more than four senses such as olefin(e) acid ester.
As the ProductName of commercially available (methyl) acrylate compounds, such as, can enumerate NEOMER DA-600 (Sanyo Chemical Industries, Ltd.'s manufacture), Aronix M-309, M-7100, M309 (east Sub-synthesis Co., Ltd. manufactures), A-DCP (manufacture of chemical industry Co., Ltd. of Xin Zhong village), 1.6HX-A (common prosperity chemical industry Co., Ltd. manufacture), FA-125 (Hitachi Chemical Co., Ltd.'s manufacture) etc..
The above-mentioned monomer with (methyl) acryloyl group can be used alone a kind, it is also possible to is applied in combination 2 More than Zhong.
In the present invention, be preferably used multifunctional containing (methyl) acryl monomer, especially trifunctional with On containing (methyl) acryl monomer, thus, the monomer composition of the present invention is coated substrate etc. Base material also carries out solidifying and heat resistance, hardness and resistance toization of solidfied material (film after solidification) that obtain It is the best for learning medicine.
[containing the compound of NCO]
In the present invention, as the compound containing NCO, it is possible to use aliphatic/ester ring type isocyanide Acid esters, aromatic isocyanate and blocked isocyanate.
Polyfunctional isocyanate is preferably used in the present invention.This is because, when using polyfunctional isocyanate, Can form the network structure with triazine skeleton, therefore heat resistance, chemical proofing etc. improve further.
This aliphatic/ester ring type isocyanates, aromatic isocyanate compounding amount relative to 100 mass parts The monomer with (methyl) acryloyl group is 2~100 mass parts, preferably 2~50 mass parts.
It addition, the compounding amount of blocked isocyanate has (methyl) acryloyl group relative to 100 mass parts Monomer be 2~200 mass parts.During less than 2 mass parts, it is impossible to obtain sufficient Thermocurable, it is impossible to obtain Obtain adaptation, chemical proofing, heat resistance.During more than 200 mass parts, containing of acryl monomer Quantitative change is few, ultra-violet solidified difference.
As above-mentioned aliphatic/ester ring type isocyanate compound, such as, have 1,6-hexa-methylene two isocyanic acid Ester (HDI or HMDI), IPDI (IPDI), hexahydrotoluene 2,4-(2,6)-two are different Cyanate (hydrogenation TDI), 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) (hydrogenation MDI), 1,3-(isocyanide Acid group closes methyl) hexamethylene (hydrogenation XDI), ENB diisocyanate (NDI), lysine two is different Cyanate (LDI), trimethyl hexamethylene diisocyanate (TMDI), dimer acid diisocyanate (DDI), N, N ', N "-three (6-isocyanato-hexa-methylene) biuret etc..
As above-mentioned aromatic isocyanate compound, such as can enumerate toluene di-isocyanate(TDI) (TDI), 4,4 '-methyl diphenylene diisocyanate (MDI), XDI (XDI) etc..
In the present invention, these isocyanates can arbitrarily be used alone one of which, it is possible to use 2 kinds Above.
In addition it is also possible to use 1, the tripolymer of 6-hexamethylene diisocyanate, isophorone two isocyanide The tripolymer of acid esters.
It addition, liquefaction and the sight of shelf-life of the monomer composition from the manufacture method of the present invention Point sets out, and isocyanate compound is preferably used and has carried out end-blocking with known end-capping reagent (sealer) Blocked isocyanate.
As the ProductName of commercially available blocked isocyanate, such as, can enumerate BI7961, BI7992 (all Manufacture for Baxenden company), MF-K60X (Asahi Chemical Corp's manufacture), VPLS2253, BL4265SN (being Sumika Bayer Urethane Co., Ltd. to manufacture) etc..
[end-capping reagent]
As end-capping reagent, such as, can enumerate ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol etc. Alcohols, the phenols such as phenol, chlorophenol, cresols, xylenol, p-nitrophenol, p-t-butyl phenol, To sec-butyl phenol, to the alkylbenzene phenols such as sec-amyl phenol, POP, nonylphenol, 3- The basic nitrogen compounds such as pyridone, 8-hydroxyquinoline, 8-hydroxyl quinaldine, diethyl malonate, Ethyl acetoacetate, acetylacetone,2,4-pentanedione isoreactivity methylene compound, acetamide, acrylamide, acetophenone The amide-types such as amine, the acid imide such as succimide, maleimide, 2-ethyl imidazol(e), 2-ethyl-4- The imidazoles such as methylimidazole, pyrazoles, 3-methylpyrazole, 3, the pyrazoles such as 5-dimethyl pyrazole, 2-pyrrolidines The lactams such as ketone, epsilon-caprolactams, the ketoxime such as acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, acetaldoxime Or aldoxime class, ethylenimine, bisulfites etc..
As blocked isocyanate, it is preferably with at least appointing in activity methene compound and pyrazoles Anticipate a kind of end-blocking isocyanates blocked, more preferably with diethyl malonate and 3,5-diformazan The most any a kind of end-blocking isocyanates blocked in base pyrazoles, particularly preferably with 3,5- The end-blocking isocyanates that dimethyl pyrazole is blocked.
Above-mentioned end-capping reagent can be used singly or in combination of two or more, it is also possible to uses single Solely or the multiple blocked isocyanate of two or more blocking agent.
[Photoepolymerizationinitiater initiater]
It addition, the monomer composition used in the present invention can contain Photoepolymerizationinitiater initiater further.As light Polymerization initiator, as long as can make (methyl) acrylate polymerization occur just by the irradiation of energy-ray Have no particular limits, it is possible to use radical polymerization initiator.
As optical free radical polymerization initiator, as long as utilize light, laser, electron beam etc. to produce free radical And cause the compound of Raolical polymerizable, the most all can use.Draw as the polymerization of this optical free radical Send out agent, such as, can enumerate the benzene such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether Acyloin and benzoin alkyl ethers;Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy The acetophenones such as base-2-phenyl acetophenone, 1,1-dichloroacetophenone;2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2- Morpholinopropane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, N, N- The aminoacetophenone classes such as dimethylamino benzoylformaldoxime;2-methylanthraquinone, 2-EAQ, 2-tert-butyl anthracene The Anthraquinones such as quinone, 1-chloroanthraquinone;2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, CTX, The thioxanthene ketones such as 2,4-diisopropylthioxanthone;Acetophenone dimethyl ketal, benzil dimethyl ketal etc. Ketal class;2,4,5-triarylimidazoles dimer;Hibon;2-mercaptobenzimidazole, 2-sulfydryl The mercaptan compound such as benzothiazole, 2-mercaptobenzothiazole;2,4,6-tri--s-triazine, 2,2,2-ethobrom, The organohalogen compounds such as trisbromomethyl benzene sulfone;Benzophenone, 4,4 '-bis-diethylamino benzophenone etc. Benzophenone or xanthones;2,4,6-trimethyl benzoyl diphenyl base phosphine oxide etc..
Above-mentioned optical free radical polymerization initiator can be used alone or mix multiple use.
It addition, in addition, it is also possible to use N, N-dimethyl amino benzoate, N, N-dimethyl The tertiary amines such as aminobenzoic isoamyl valerate, 4-dimethylaminobenzoic acid pentyl ester, triethylamine, triethanolamine Etc. light-initiated auxiliary agent.It addition, in order to promote light reaction, it is also possible to add in optical free radical polymerization initiator The titanocenes of (BASF JAPAN LTD. manufactures) such as the CGI-784 having absorption in being added in visible region Compound etc..It should be noted that the composition being added in optical free radical polymerization initiator is not limited to above-mentioned, As long as absorbing light in ultraviolet light or visible region, and the unsaturated groups such as (methyl) acryloyl group are made to enter Row radical polymerization, then be not limited to Photoepolymerizationinitiater initiater, light-initiated auxiliary agent, can be used alone or in combination Multiple use.
The compounding amount of Photoepolymerizationinitiater initiater has the monomer of (methyl) acryloyl group relative to 100 mass parts It is 0.5~15 mass parts, more preferably 0.5~10 mass parts, it is further preferred that 1~10 mass parts.
As the ProductName of commercially available Photoepolymerizationinitiater initiater, such as can enumerate Irgacure907, Irgacure127 (being BASF JAPAN LTD. to manufacture) etc..
[other additive]
In the monomer composition of the present invention, froth breaking/levelling agent, thixotropy conferring agents can be contained as required The additives such as/thickener, coupling agent, dispersant, fire retardant.
As defoamer/levelling agent, it is possible to use organosilicon, modified organic silicon, mineral oil, vegetable oil, Aliphatic alcohol, aliphatic acid, metallic soap, fatty acid amide, polyether polyols, polyoxy alkylidene alkane The compounds etc. such as base ether, polyoxyalkylene fatty acid esters.
As thixotropy conferring agents/thickener, it is possible to use kaolin, montmorillonite (smectite), illiteracy are de- Viscosity mineral or the particulate titanium dioxide such as soil (montmorillonite), bentonite, talcum, mica, zeolite Silicon, silica gel, amorphous inorganic particle, polyamide-based additive, modified urea system additive, wax system add Agent etc..
By adding froth breaking/levelling agent, thixotropy conferring agents/thickener, it is possible to special to the surface of solidfied material The proterties of property and composition is adjusted.
About coupling agent, it is possible to use: as alkoxyl have methoxyl group, ethyoxyl, acetyl group etc. and As reactive functional groups, there is vinyl, methylacryloyl, acryloyl group, epoxy radicals, cyclic rings The silane of epoxide, sulfydryl, amino, diaminourea, acid anhydrides, uride base, thioether group, NCO etc. Coupling agent, the most such as vinylethoxysilane, vinyltrimethoxy silane, vinyl three (β-first Epoxide ethyoxyl) the ethene base system silanization such as silane, γ-methacryloxypropyl trimethoxy silane Compound, gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl) gamma-amino propyl trimethoxy silicon Alkane, N-β-(amino-ethyl) gamma-amino hydroxypropyl methyl dimethoxysilane, γ-ureido-propyl triethoxy The amino system silane compounds such as silane, γ-glycidoxypropyltrime,hoxysilane, β-(3,4-epoxide ring Hexyl) the epoxy silicon such as ethyl trimethoxy silane, γ-glycidoxypropyl diethoxy silane The sulfydryl such as hydride compounds, γ mercaptopropyitrimethoxy silane system silane compound, Ν-phenyl-gamma-amino third The silane couplers such as phenylamino base system silane compound such as base trimethoxy silane;Isopropyl three isostearoyl Change titanate esters, four octyl groups double (two-tridecyl phosphite) titanate esters, double (dioctylphyrophosphoric acid Ester) ethoxyacetic acid ester titanate esters, isopropyl three-dodecyl benzenesulfonyl titanate esters, isopropyl three (two Octyl group pyrophosphate) titanate esters, tetra isopropyl double (dioctyl phosphito ester) titanate esters, four (1,1- Diene propoxy methyl-1-butyl)-bis-(two-tridecyl) phosphite ester titanate esters, double (dioctyl Pyrophosphoric acid ester group) ethylene titanate esters, isopropyl three caprylyl titanate esters, isopropyl Dimethylacryloyl Isostearoyl base titanate esters, isopropyl three stearyl two acryloyl group titanate esters, (two is pungent for isopropyl three Base phosphate) titanate esters, isopropyl three cumyl phenyl titanate esters, dicumylphenyl ethoxyacetic acid ester metatitanic acid The titanate esters system coupling agents such as ester, two isostearoyl base ethylidene titanate esters;Containing olefinic unsaturation zirconate Compound, the compound containing new alkoxy zirconium ester, the new trineodecanoyl zirconate of new alkoxyl three, new alcoxyl Base three (dodecyl) benzenesulfonyl zirconate, new alkoxyl three (dioctyl) Zirconium phosphoester acid esters, New alkoxyl three (dioctyl) pyrophosphate zirconate, new alkoxyl three (ethylene amino) ethyl Zirconate, new alkoxyl three (amino) phenyl zirconate, four (2,2-diene propoxy methyl) fourth Base-two (two-tridecyl) phosphite ester zirconate, the new caprinoyl of neopentyl (diallyl) epoxide-three Base zirconate, neopentyl (diallyl) epoxide-three (dodecyl) benzenesulfonyl zirconate, new Amyl group (diallyl) epoxide-three (dioctyl) Zirconium phosphoester acid esters, neopentyl (diallyl) Epoxide-three (dioctyl) pyrophosphate zirconate, neopentyl (diallyl) epoxide-three (N-Asia second Base diaminourea) ethyl zirconate, neopentyl (diallyl) epoxide-three (amino) phenyl zirconic acid Ester, neopentyl (diallyl) epoxide-trimethacrylate acyl group zirconate, neopentyl (diallyl) Epoxide-triacryl zirconate, di neo-pentyl (diallyl) epoxide-two p-benzoyl base zirconium Double (the 2-third of acid esters, di neo-pentyl (diallyl) epoxide-two (3-sulfydryl) propionic acid zirconate, 2,2- Enol closes methyl) butanol base-ring two [2,2-(double 2-propenyls close methyl) butanol base] pyrophosphate-O, O- Zirconium (IV) (Zirconium IV 2,2-bis (2-propenolatomethyl) butanolato, cyclo-di-[2,2- (bis2-propenolatomethyl) butanolato] pyrophosphate-O, O) etc. zirconate system coupling agent; The Aluminates such as diisobutyl (oil base) acetoacetyl aluminate, Acetacetic acid alkyl ester aluminum-diisopropoxide It it is coupling agent etc..
As dispersant, it is possible to use polycarboxylic-acid, naphthalenesulfonic acid formalin condensation system, polyethylene glycol, The high-molecular type dispersing agents such as polycarboxylic acids part Arrcostab system, polyethers system, polyalkylene polyamine system, alkyl sulphur The low molecule type dispersions such as acid system, quaternary ammonium system, higher alcohol epoxy methane series, polyol ester system, alkylated polyamines system Agent etc..
As fire retardant, it is possible to use the hydrated metal such as aluminium hydroxide, magnesium hydroxide system, red phosphorus, phosphoric acid Ammonium, ammonium carbonate, Firebrake ZB, zinc stannate, molybdenum compound system, bromine compounds system, chlorine compound system, phosphorus Acid esters, phosphorus-containing polyol, containing phosphamidon, cyanurate melamine, melamine compound, triazine chemical combination Thing, guanidine compound, organosilicon polymer etc..
And then, organic Binder Composition can be added in the monomer composition of the present invention.It addition, for adjusting Whole polymerization speed, the degree of polymerization, it is possible to add polymerization inhibitor, retarder.
Can be to be colored as purpose interpolation coloring pigment, dyestuff etc. in the monomer composition of the present invention.Make For coloring pigment, dyestuff etc., can use in order to lower pigment concordance list show known in usual coloring pigment, Dyestuff.
Such as can enumerate pigment blue 15,15:1,15:2,15:3,15:4,15:6,16,60, solvent Blue 35,63,68,70,83,87,94,97,122,136,67,70, pigment Green 7,36,3, 5,20,28, solvent yellow 16 3, pigment yellow 24,108,193,147,199,202,110,109, 139、179、185、93、94、95、128、155、166、180、120、151、154、156、 175、181、1、2、3、4、5、6、9、10、12、61、62、62:1、65、73、74、75、 97、100、104、105、111、116、167、168、169、182、183、12、13、14、 16、17、55、63、81、83、87、126、127、152、170、172、174、176、188、 198, pigment orange 1,5,13,14,16,17,24,34,36,38,40,43,46,49, 51,61,63,64,71,73, paratonere 1,2,3,4,5,6,8,9,12,14,15, 16、17、21、22、23、31、32、112、114、146、147、151、170、184、187、 188、193、210、245、253、258、266、267、268、269、37、38、41、48:1、 48:2、48:3、48:4、49:1、49:2、50:1、52:1、52:2、53:1、53:2、57:1、58:4、 63:1、63:2、64:1、68、171、175、176、185、208、123、149、166、178、 179、190、194、224、254、255、264、270、272、220、144、166、214、 220,221,242,168,177,216,122,202,206,207,209, solvent of red 135, 179,149,150,52,207, pigment violet 19,23,29,32,36,38,42, solvent violet 13, 36, pigment brown 23,25, pigment black 1,7 etc..These coloring pigment dyestuffs etc. are relative to 100 mass parts Monomer composition preferably adds 0.01~5 mass parts.It addition, be used for marking by the monomer composition of the present invention In the case of purposes, preferably add the titanium oxide of rutile-type, Detitanium-ore-type for guaranteeing visibility.This In the case of Zhong, relative to 100 mass parts monomer compositions, preferably add 1~20 mass parts.These colorings Pigment/dyes etc. can be used alone or in combination two or more and use.
And then, in the monomer composition of the present invention, it is possible to use for adjusting the solvent of viscosity, but be Preventing the thickness after solidification from reducing, addition is preferred less.It addition, more preferably do not contain for adjusting The solvent of viscosity.
When the monomer composition of the present invention contains Photoepolymerizationinitiater initiater, by irradiation ultraviolet radiation, electron beam, Chemical ray isoreactivity energy-ray, makes (methyl) acrylate carry out photocuring, thereafter, by such as Heat described on, (methyl) acrylate can be made to be polymerized.
Therefore, make to coat the monomer composition of the base materials such as substrate by the photocuring irradiated based on light, with And ensuing heat cure the two stage based on heating and solidify, workability and said curing General each characteristic of thing improves.
In the present invention, when monomer composition is fully cured, it is possible to use known heater means, the hottest The heating furnaces such as wind furnace, electric furnace, infrared induction heating furnace.
The transparency of poly-(methyl) acrylate that manufactured by the manufacture method of the present invention, plasticity, resistance to The excellences such as impact, adaptation, chemical proofing, heat resistance and insulating properties, therefore can be suitably used for many Plant purposes.Such as, in addition to window materials for the vehicles such as building, vehicle etc., also can fit For electric/electronic, commodity, office appliance etc., particularly preferred for needs resistance to impact, close Conjunction property, chemical proofing, heat resistance and the product such as printed circuit board (PCB) of insulating properties.
It should be noted that the present invention is not limited to technical scheme and the enforcement of above-mentioned embodiment Example, can carry out various deformation in the range of the main idea of invention.
Embodiment
I. hot set test
[embodiment 1~11 and comparative example 1~4]
Each composition is compounded in the ratio shown in table 1, it is obtained the present invention's with dissolvers stirring Monomer composition and compare monomer composition.
[gel time mensuration]
For the monomer composition of the present invention, (day, new science Co., Ltd. manufactured to use gelation testing machine Gelation testing machine), heat the most at an established temperature, measure until gelation Till time.By result record in Table 1.
[table 1]
The compounding amount of each material in table is in units of mass parts.
Gel time refers to lose flowability to material from beginning to warm up monomer composition and solidifies Time (measured by gelation testing machine, in seconds).
It should be noted that the details of material described in table 1 is as follows.
Acrylate 1: trimethylolpropane trimethacrylate (TMPTA)
Toagosei Co., Ltd manufactures M-309
Acrylate 2: Tricyclodecane Dimethanol diacrylate
KCC of Xin Zhong village manufactures A-DCP
Acrylate 3:1,6-hexanediyl ester
Kyoeisha Chemical Co., Ltd. manufactures 1.6HX-a
Acrylate 4: neopentylglycol diacrylate
Hitachi Chemical Co., Ltd. manufactures FA-125M
Isocyanates 1 a: xylylene diisocyanate
Isocyanates 2: IPDI
Isocyanates 3:1,6-hexamethylene diisocyanate
Blocked isocyanate 1:Baxenden company manufacture BI7961
Solid constituent 70% NCO composition 10.2%
The biuret body dimethylpyrazole of 1,6-hexamethylene diisocyanate Material
Blocked isocyanate 2:Baxenden company manufacture BI7992
Solid constituent 70% NCO composition 9.2%
The tripolymer dimethyl pyrazole of 1,6-hexamethylene diisocyanate and (activity methene compound) The material of diethyl malonate end-blocking
Blocked isocyanate 3: Asahi Chemical Corp manufactures MF-K60X
Solid constituent 60% NCO composition 6.6%
The material of 1,6-hexamethylene diisocyanate activity methene compound end-blocking
Blocked isocyanate 4:Sumika Bayer Urethane Co., Ltd. manufactures VPLS2253
Solid constituent 75% NCO composition 10.5%
The material of the tripolymer dimethylpyrazole of 1,6-hexamethylene diisocyanate
Blocked isocyanate 5:Sumika Bayer Urethane Co., Ltd. manufactures BL4265SN
Solid constituent 65% NCO composition 8.1%
The material that the tripolymer of IPDI is blocked by methyl ethyl ketoxime
By measuring gel time, for the composition of embodiment 1~8, the feelings carried out at 150 DEG C Under condition, 21 seconds used times~complete the polymerization of acrylate for 590 seconds.
On the other hand, in the comparative example 1 without isocyanates, even if carrying out the test of more than 1000 seconds, The most there is not gelation.
It addition, in the composition of embodiment 9~11, maximum with generation gelation in 926 seconds, polymerisation Complete.On the other hand, in comparative example 2~4, though the test of longer more than 2000 seconds of the time of carrying out, The most there is not gelation.It follows that under the acryloyl group the coexisting with isocyanates, i.e. can under low temperature React, but do not react when there is not isocyanates.
[mensuration of DSC data]
About embodiment 1 and the composition of comparative example 1, Seiko Electronics Co., Ltd is used to manufacture EXSTAR, carries out means of differential scanning calorimetry mensuration (DSC).The DSC curve obtained is shown in Fig. 1.
Its result understands: with the exothermic peak phase of the simple trimethylolpropane trimethacrylate of comparative example 1 Ratio, the trimethylolpropane trimethacrylate of embodiment 1 and an isocyanates (xyxylene two isocyanic acid Ester) the exothermic peak of composition move to low temperature side, it can solidify at low temperatures.
This DSC measurement result illustrates the peak of the polymerization produced in embodiment 1 and comparative example 1 indirectly, its Consistent with above-mentioned gel time measurement result, therefore it can be concluded that occurred by gelation The polymerization of acrylate.
[mensuration of ir spectrophotometry]
For the composition of embodiment 1, use the Spectrum100 that Perkin Elmer Japan Ltd. manufactures, Absorbance (absorption) is measured by infrared spectrophotometer (IR Spectroscopy).Need Bright, as MacroATR unit, employ smiths Dura Sampl IRII.
This mensuration is carried out for following sample: first, is coated with by the composition of embodiment 1 with scraper On 2 KBr plates, by wherein one in atmosphere with 30 minutes (sample 1) of 80 DEG C of heating, by another In atmosphere with 30 minutes (sample 2) of 150 DEG C of heating.
The IR spectrogram recording sample 1 illustrates above Fig. 2, and the IR spectrogram recording sample 2 exists The lower section of Fig. 2 illustrates.
Sample 1, compared with the IR spectrogram of sample 2, represents the 2260cm of NCO-1Neighbouring peak exists In the collection of illustrative plates of sample 1 (80 DEG C of heating) substantially, significantly subtract in the collection of illustrative plates of sample 2 (150 DEG C of heating) Few.
And then, represent the 1406cm of acryloyl group-1Neighbouring peak is in the collection of illustrative plates of sample 1 (80 DEG C of heating) Substantially, it is greatly decreased in the collection of illustrative plates of sample 2 (150 DEG C of heating).
It follows that isocyanates is consumed under heating with acryloyl group.
Additionally it is observed that compared with sample 1 (80 DEG C of heating), 1721cm-1The peak of neighbouring carbonyl Sample 2 (150 DEG C of heating) increases.
This shows that NCO generation trimerization generates carbonyl.
Measurement result shown in integrated survey Fig. 1 and Fig. 2, it may be said that by isocyanates and propylene Heat under the coexisting state of acid esters, thus the trimerization of isocyanates occurs, with the reaction phase of this trimerization Companion, there occurs the polymerization of acrylate.
II. photo-thermal use solidity test
[embodiment 12,13, and comparative example 5]
1. ultraviolet irradiation process
In the ratio shown in table 2, each composition is compounded, it is obtained this with dissolvers stirring Bright monomer composition and compare monomer composition.
[table 2]
Embodiment 12 Embodiment 13 Comparative example 5
Acrylate 1 60 60 60
Photoepolymerizationinitiater initiater 1 3 3 3
Photoepolymerizationinitiater initiater 2 3 3 3
Isocyanates 1 10 - -
Blocked isocyanate 2 - 60 -
Levelling agent 0.1 0.1 0.1
It should be noted that the details of material described in table 2 is as follows.
Acrylate 1: trimethylolpropane trimethacrylate (TMPTA)
Toagosei Co., Ltd manufactures M-309
Photoepolymerizationinitiater initiater 1:BASF JAPAN LTD. manufactures Irgacure907
Photoepolymerizationinitiater initiater 2:BASF JAPAN LTD. manufactures Irgacure127
Isocyanates 1 a: xylylene diisocyanate
Blocked isocyanate 2:Baxenden company manufacture BI7992
Solid constituent 70%NCO composition 9.2% (1,6-hexamethylene diisocyanate active methylene group The material of compound end-blocking)
Levelling agent: BYK JAPAN LTD. manufactures BYK-307
[making of test sample]
A. ultraviolet irradiation sample: FR-4/10 μ
The following uncured sample making several each tests: by monomer composition and the ratio of the present invention Relatively monomer composition is on the FR-4 copper-clad laminated board (substrate) of 150mm × 95mm × 1.6mm, logical Cross bar coater to be coated in the way of thickness reaches 10 μm, thus make uncured sample.To these Uncured sample high voltage mercury lamp radiation accumulated light is 150mJ/cm2Ultraviolet.
Under carrying out for each sample (ultraviolet irradiation sample: FR-4/10 μ) after ultraviolet irradiation process State fitness test, pencil hardness test, chemical proofing test, heat resistant test.By result of the test Record is in table 3.
B. ultraviolet irradiates/heats sample: FR-4/10 μ
Utilize heated air circulation type drying oven that ultraviolet irradiates sample: FR-4/10 μ heats 30 at 150 DEG C Minute, obtain ultraviolet irradiate/heating after sample (ultraviolet irradiate/heat sample: FR-4/10 μ). This sample is carried out following fitness test, pencil hardness test, chemical proofing test and heat-resisting Test.By logging in table 4.
C. ultraviolet irradiates/heats sample: B COUPON/40 μ
By the monomer composition of the present invention and compare monomer composition and be applied to IPC with thickness 40 μm On comb-type electrode B COUPON (substrate) of B-25 test pattern, carry out ultraviolet same as described above Irradiate, then carry out heating same as described above, thus obtain the sample that ultraviolet irradiates/heats: B COUPON/40μ.It is carried out following insulating properties test.
Above-mentioned each sample is carried out attribute testing shown below.
[1. fitness test]
Film coated surface cutter in each sample cut 11 joint-cuttings with 1mm interval, in length and breadth by film Paste adhesive tape on 100 cutting zones that the joint-cutting in length and breadth on surface surrounds, peel off, check not Peeled off by adhesive tape and residue in the number of the cutting zone of the film of FR-4.
[2. pencil hardness test]
Make each sample, carry out according to JISK5400, the Hi-uni using Mitsubishi Pencil K. K to manufacture The mensuration of pencil hardness test.
Specifically, cutting the timber portion of pencil, exposed length is the pen core of 5~6mm.Use Pen core front end is ground to smooth at sand paper and forms the pencil of circular cross-section.By this pencil with sample table Face is that the angle of 45 degree keeps, and applies the load of 1kg, with the angles of 45 degree at film on sample surfaces On scratch.By the highest hardness record of non-for film scratch to the pencil of substrate in table 2.
[3. chemical proofing test]
Make each sample impregnate 30 minutes under room temperature in the aqueous sulfuric acid of 10%, after being drawn off, carry out water Wash, be dried.After the painting membrane stage of dried each sample is carried out visual valuation, with Cellotape (note Volume trade mark) peel off, it is carried out as follows evaluation.
Zero: the state of film is entirely without change.
×: film has and floats, peels off.Or, exist and be significantly transferred to Cellotape (registration mark) Stripping.
[4. heat resistant test]
Each sample is coated with rosin series scaling powder (SF-270 that Sanwa Chemical Co., Ltd manufactures), The solder bath of 260 DEG C impregnates 10 seconds.After each sample being taken out from solder bath and naturally cooling down, use Propylene glycol methyl ether acetate washs, is dried.Painting after this test repeats 3 times, to each test film After the state of film carries out visual valuation, peel off with Cellotape (registration mark), be carried out as follows Evaluate.
Zero: the state of film is entirely without change.
△: be visually not changed in, has some strippings when peeling off with Cellotape (registration mark).
×: film has and floats, peels off.Or, exist and be significantly transferred to Cellotape (registration mark) Stripping.
[5. insulating properties test]
For aforesaid ultraviolet irradiation sample: B COUPON/40 μ, apply the bias of DC500V, Measure insulating resistance value.It is carried out as follows evaluation.
Zero: insulating resistance value >=100G Ω
×: insulating resistance value < 100G Ω
A. ultraviolet irradiation sample: the result of the test of FR-4/10 μ
(chemical proofing is tested, and heat-resistance test for fitness test, pencil hardness test)
[table 3]
Embodiment 12 Embodiment 13 Comparative example 5
1. fitness test 0/100 0/100 0/100
2. pencil hardness test H H H
3. chemical proofing test × × ×
4. heat-resistance test × × ×
B. ultraviolet irradiates/heats sample: the result of the test of FR-4/10 μ
(fitness test, pencil hardness test, chemical proofing are tested and heat-resisting Property test)
C. ultraviolet irradiates/heats sample: the result of the test (insulating properties test) of B COUPON/40 μ
[table 4]
Embodiment 12 Embodiment 13 Comparative example 5
1. fitness test 100/100 100/100 0/100
2. pencil hardness test 5H 3H H
3. chemical proofing test ×
4. heat-resistance test ×
5. insulating properties test -
-: do not evaluate
According to above-mentioned table 4 it will be apparent that, the film obtained by the manufacture method of the present invention/solidfied material tool There is the performance that adaptation, hardness, chemical proofing, heat resistance and insulating properties are all excellent.
It should be noted that the present invention is not limited to technical scheme and the embodiment of above-mentioned embodiment, Various deformation can be carried out in the range of invention main idea.

Claims (6)

1. the manufacture method of poly-(methyl) acrylate, it is characterised in that will be to having (methyl) The monomer of acryloyl group adds the monomer composition having the compound of NCO and obtain exist Heat at 140 DEG C to 170 DEG C so that described in there is (the first of monomer of (methyl) acryloyl group Base) acryloyl group is polymerized, described in have that the monomer of (methyl) acryloyl group do not has can be with different The functional group of polyisocyanate reactant.
Manufacture method the most according to claim 1, it is characterised in that also to described monomer composition Middle interpolation Photoepolymerizationinitiater initiater, irradiate active energy beam so that described in there is (methyl) acryloyl The monomer of base carries out photocuring, then by described heating make described in there is the list of (methyl) acryloyl group Body is polymerized.
3. poly-(methyl) acrylate, it is characterised in that it is by claim 1 or 2 Described manufacture method obtains.
4. a monomer composition, it is characterised in that it is for the manufacture method described in claim 1.
5. a solidfied material, it is characterised in that it is to make the monomer composition described in claim 4 solidify ?.
6. a printed circuit board (PCB), it is characterised in that it has the solidfied material described in claim 5.
CN201380017235.5A 2012-03-30 2013-03-25 Poly-(methyl) acrylate and manufacture method, monomer composition, solidfied material and printed circuit board (PCB) Active CN104203992B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4117235A (en) * 1971-09-23 1978-09-26 Owens-Illinois, Inc. Novel preparation of novel low molecular weight, liquid polymer
CN1535289A (en) * 2000-11-06 2004-10-06 Method for coating substrates
CN101563382A (en) * 2006-12-19 2009-10-21 巴斯福涂料股份公司 Coating agents having high scratch resistance and weathering stability
CN102066433A (en) * 2008-06-17 2011-05-18 阿克马法国公司 Composition containing (meth)acrylic polymer and copolymer having associative groups

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6131449A (en) 1984-07-23 1986-02-13 Nippon Kayaku Co Ltd Ultraviolet-curing resin composition
JP2002174892A (en) * 2000-12-07 2002-06-21 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element, method for producing resist pattern and method for producing printed wiring board
JP2008094913A (en) 2006-10-10 2008-04-24 Toray Fine Chemicals Co Ltd One-component radically curable adhesive composition
US8178204B2 (en) * 2008-03-05 2012-05-15 Bayer Materialscience Llc Acrylate-modified aspartates and gel coat compositions made therefrom
JP5422195B2 (en) * 2008-12-18 2014-02-19 リンテック株式会社 Release agent and release sheet
JP2010212516A (en) * 2009-03-11 2010-09-24 Mitsubishi Paper Mills Ltd Crosslinking composition for manufacturing screen printing mask with resin
CN102666971B (en) * 2009-11-20 2014-12-17 大金工业株式会社 Fluoropolymers and treatment agent
DE102009055061A1 (en) * 2009-12-21 2011-06-22 Evonik Degussa GmbH, 45128 New initiation procedure for the polymerization of (meth) acrylates
KR20130124359A (en) * 2011-01-27 2013-11-13 가부시키가이샤 오토네트웍스 테크놀로지스 Chain transfer agent, photosensitive composition, cured product of photosensitive composition, and method for curing photosensitive composition
JP5802396B2 (en) * 2011-01-27 2015-10-28 株式会社オートネットワーク技術研究所 Ultraviolet curable composition and cured product using the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4117235A (en) * 1971-09-23 1978-09-26 Owens-Illinois, Inc. Novel preparation of novel low molecular weight, liquid polymer
CN1535289A (en) * 2000-11-06 2004-10-06 Method for coating substrates
CN101563382A (en) * 2006-12-19 2009-10-21 巴斯福涂料股份公司 Coating agents having high scratch resistance and weathering stability
CN102066433A (en) * 2008-06-17 2011-05-18 阿克马法国公司 Composition containing (meth)acrylic polymer and copolymer having associative groups

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