CN103087276B - Active energy ray curable resin, resin combination, hard paint, cured film, decorating film and injection-moulding plastic product - Google Patents
Active energy ray curable resin, resin combination, hard paint, cured film, decorating film and injection-moulding plastic product Download PDFInfo
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- CN103087276B CN103087276B CN201210425440.2A CN201210425440A CN103087276B CN 103087276 B CN103087276 B CN 103087276B CN 201210425440 A CN201210425440 A CN 201210425440A CN 103087276 B CN103087276 B CN 103087276B
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- active energy
- parts
- energy ray
- methyl
- composition
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- 238000004090 dissolution Methods 0.000 description 1
- GEJJECIDFXFUMI-UHFFFAOYSA-N dodecanethioic s-acid Chemical compound CCCCCCCCCCCC(S)=O GEJJECIDFXFUMI-UHFFFAOYSA-N 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
Abstract
The present invention provides a kind of active energy ray curable resin, resin combination, hard paint, cured film, decorating film and injection-moulding plastic product.With in decorating film in mould, improved by making the processability in injection moulding, obtain the injection-moulding plastic product on the surface with excellent hard painting propert, take into account ductility high and high rigidity, and low sticky desciccator diaphragm is formed in the case where optical characteristics is not damaged.A kind of active energy ray curable resin, weight average molecular weight is 10000 ~ 100000, by making α, β unsaturated carboxylic acids (C) and the following copolymer reaction with branched structure and obtain, the copolymer pass through to make (methyl) acrylic ester monomer (A) containing epoxy radicals and any one end there is unsaturated double-bond and do not contain epoxy radicals and carboxyl weight average molecular weight 1000 ~ 20000 macromonomer (B) with weight ratio (A):(B) it is 80:20~40:60 are reacted and are obtained.
Description
Technical field
Applied firmly the present invention relates to the active energy ray curable resin with processability, active energy ray curable
Agent, the cured film using them, the decorating film for being laminated with cured film and the injection-moulding plastic product using decorating film.More specifically
For, it is not intended to the two-dimensional decoration such as application, printing method but carries out the resins such as plastics in mould (In Mold)
Injection moulding while method, the i.e. in-mold decoration (In Mold Decorating), the in-mold transfer printing (In that are decorated
MoldTransfer), in-mold labels (In Mold laminating), in-molded (In Mold Forming), film insertion
The hard paint of active energy ray curable that is used in the decorating film of shaping (Film Insert Molding) etc. and use
The article of its shaping.
Background technology
In recent years, for injection-moulding plastic product such as mobile phone terminal, PC housing and in-car interior trim panels
Speech, it is desirable to take into account the design of complexity and the difficult scratch resistant of plastic molded article.Therefore, with the two-dimensional decoration such as atomized spray painting and printing
Method is compared, can realize complexity pattern and can with colourful style improve design in-mold decorative method it is standby
Attract attention.In-mold decorative method refers to following method：It is built into for the surface reality to products formed in mould in injection moulding
The decorating film of decoration is applied, the plastic resin after injection melting makes its integration, and plastic molded article surface is implemented to decorate, according to
The composition of decorating film, can be categorized as following (1) and (2).A kind of method (being referred to as in-mold decoration etc.) is：(1) using in stripping
The decorating film of hard conating and patterned layer etc. is laminated with base material, is inserted in mould, after injection moulding, peeling base shelled
From residual hard conating and the patterned layer on plastic molded article surface.Another method (being referred to as IMF etc.) is：(2) will be in PET
Patterned layer is provided with (polyethylene terephthalate) film and the decorating film of hard conating is inserted in mould, be injected into
Type, is attached on plastic molded article.
It is that in-mold decoration film is extended into along mould when injection moulding is carried out in mould for above-mentioned (1), (2)
The shape of inner surface.Generally, based on hard painting propert, hard and crisp proterties is obtained, stress during due to extending is easy
Crack.Specifically, easily cracked in the deep-draw deep of three-dimension curved surface and acute angle corner portions, for the processing of decorating film
Property for, hard painting propert reduction or design are limited.
In recent years, in order to realize the differential of product, complication for design and the requirement of scratch resistant is more difficult to, is taken into account
Processability is indispensable with hard painting propert, in this regard, proposing various methods.For example, it is proposed that by (first more than trifunctional
Base) acrylic acid oligomer and function ~ bis- function (methyl) acrylic monomers the method for controlling crosslink density with being combined into
(with reference to patent document 1).According to the method, although deformation when proposing with high surface hardness and can follow shaping
The hard coat film of processability, but case hardness and processability are in trade-off relationship, so that in the presence of having to a certain degree of balance
And the problem compromised.
Further it is proposed that following method：(methyl) the acryloyl group equivalent for coordinating molecular weight 5000 ~ 50000 is 200g/eq
Above and below 800g/eq polymer (methyl) acrylate and molecular weight 1000 ~ 10000 (methyl) acryloyl group work as
Measure as 100g/eq is (literary with reference to patent less than the method for polyfunctional carbamate (methyl) acrylate of 200g/eq
Offer 2).According to the method, for the method for above-mentioned (1), wear resistance and chemical-resistant are excellent, and in products formed
Curvature portion will not crack.But, for the method for above-mentioned (2), do not meet processability.
And then, it is also proposed that coordinate non-without free-radical polymerised double bond by (methyl) acrylate monomer
Reaction resin assigns the method (with reference to patent document 3) of processability.But, coordinating such non-reacted resin, increasing
In the case of plastic resin, although processability is improved, but can not meet hard painting propert high required in recent years.
So, various researchs have been carried out for any one method of above-mentioned (1) and (2), but these researchs are only
Make the method that hard conating limbers up, generate the other problemses of the hard painting propert reductions such as the original required difficult scratch resistant of hard conating.
Not yet propose the active-energy resin with processability and hard painting propert.
On the other hand, in the case of being coated with active energy ray-curable resin on the thermoplastic film, coating is with organic molten
Active energy ray curable resin after agent regulation viscosity, makes organic solvent volatilize, after forming desciccator diaphragm, sometimes by heating
Temporarily coil into drum preservation.Now, the situation that the conveying roller of the coating machine for the purpose of being conveyed by film is contacted with desciccator diaphragm
Under, if the adhesion strength of desciccator diaphragm is high, adheres to sometimes on roller and obstacle is produced to manufacturing process.In addition, after preservation is batched
Reel during, adhesion desciccator diaphragm in the inside side of film is difficult to peel off (referred to as adhesion) from reel sometimes.By such drying
The adhesion strength of film is referred to as sticky (タ Star Network), when sticky high, easily causes above mentioned problem, phase after-tack to be difficult to cause when low
Problem is stated, operability is good, is favorably improved manufacture efficiency and yield rate.
In order to prevent problem as described above, it is proposed that coordinate titanium dioxide by active energy ray curable resin
The inorganic particles of silicon etc. reduce the contact area of interlayer so as to form concavo-convex in film coated surface, thus make sticky reduction, prevent
Only adhesion (patent document 4).
Although the method for suppressing contact area is highly effective, in order to form concavo-convex on the surface of particle, it is necessary to will apply
Film thickness is set as below particle diameter, it is necessary to thinning film, therefore, it is impossible to sufficient hard painting propert is assigned, further, since coordinating inorganic
Particulate, therefore, cured film obtains crisp physical property, is unsuitable for needing the molding film of processability.
In order to improve above mentioned problem, it is proposed that during using two kinds of each different active energy beam resins of mixed dissolution
Phase separation and concavo-convex method (patent document 5) is formed in film coated surface.Although in the case where painting thickness is not relied on
Viscosity is low and be difficult to adhesion, but due to being separated, thus infringement cured film the transparency, with inclining for optical characteristics variation
To.
Further it is proposed that the copolymer with optical polymerism functional group is organic with silica inorganic particulate on side chain
Inorganic compounding resin combination (patent document 6).When the weight average molecular weight of copolymer is 5000 ~ 100000, glued with excellent
Property, without solidifying it in machine-shaping front irradiation active energy beam, but after processing solidify it, therefore, with good
Good processability and hard painting propert, but on viscosity and processability, there is still room for improvement.
Additionally, having following record：In 100 ~ 300g/eq of (methyl) acryloyl group equivalent, hydroxyl value 20 ~ 500, Weight-average molecular
Coordinate polyfunctional isocyanate in the active energy ray-curable resin of amount 500 ~ 50000, by heating, active energy beam
There is heat cross-linking in the hydroxyl of gel-type resin, thus, suppress the viscosity of desciccator diaphragm such that it is able to suppress with polyfunctional isocyanate
Adhesion (patent document 7).But, even if hydroxyl is also carried out at normal temperatures with the reaction of isocyanates, therefore, storage stability
Difference.And, polyfunctional isocyanate's composition turns into the main cause for making that hard painting propert and viscosity are reduced sometimes.
So, not yet develop to be formed and be difficult to take into account processability and hard painting propert in trade-off relationship and do not damage in the past
The active energy ray-curable resin of the low cured film of evil optical characteristics, viscosity.
Patent document 1：Japanese Unexamined Patent Publication 2011-148964 publications
Patent document 2：Japanese Unexamined Patent Publication 2004-123780 publications
Patent document 3：Japanese Unexamined Patent Publication 2008-208154 publications
Patent document 4：Japanese Unexamined Patent Publication 2004-42653 publications
Patent document 5：Japanese Unexamined Patent Publication 2007-182519 publications
Patent document 6：Japanese Unexamined Patent Publication 2001-206925 publications
Patent document 7：Japanese Unexamined Patent Publication 10-58895 publications
The content of the invention
The present invention is a kind of active energy ray curable resin, and it is suitable for assign in recent years to plastic injection
The decorating film of the difficult scratch resistant of complicated design and products formed required by products formed, while forming a kind of low-viscosity solidification
Film, it takes into account the processability and hard painting propert being difficult in the past, and does not damage optical characteristics.
The present inventor conducts in-depth research to solve the above problems, and as a result finds, by as follows with specific
Weight average molecular weight the active energy ray curable resin that is characterized of branched structure, solve above mentioned problem, the activity
Energy ray-curable resin is obtained as follows：Make alpha, beta-unsaturated carboxylic acid (C) and by (methyl) acrylic acid by epoxy radicals is contained
Esters monomer (A) with principal component is constituted with the monomer that can be polymerized without epoxy radicals there is unsaturated double-bond in single end
Macromonomer (B) with specific weight than carry out it is free-radical polymerized obtained from A/B copolymers epoxy radicals addition and obtain
Arrive.
That is, the present invention 1 is a kind of active energy ray curable resin, and its weight average molecular weight is 10000 ~ 100000, is led to
Crossing makes α, and beta-unsaturated carboxylic acid (C) is obtained with having the copolymer reaction of branched structure as follows, and the copolymer is by making to contain
(methyl) acrylic ester monomer (A) of epoxy radicals and there is unsaturated double-bond in any one end and epoxy radicals is not contained
And the macromonomer (B) of the weight average molecular weight 1 000 ~ 20000 of carboxyl is with weight ratio (A):(B) it is 80:20~40:60 enter
Row reacts and obtains.
The present invention 2 is the active energy ray curable resin in the present invention 1, wherein, the macromonomer (B) is tool
There is the free-radical polymerized thing with free-radical polymerised group of the end structure of formula (1) expression.
(in formula, X is the compound part with free-radical polymerised group, R1It is H or CH3, R2It is-C (=O) OR3Or benzene
Base, R3 is selected from by-CH3、-CH2CH(CH3)2、-C(CH3)3And-(CH2)mCH3In the group of (m represents 1 ~ 17 integer) composition
Any one structure.N represents integer).
The present invention 3 is a kind of active energy ray-curable resin composition, is contained：Active-energy in the present invention 1 or 2
Ray curing resin and Photoepolymerizationinitiater initiater.
The present invention 4 is the active energy ray-curable resin composition of the present invention 3, wherein, also contain multifunctional (first
Base) acrylate.
The present invention 5 is a kind of hard paint of active energy ray curable, and the active energy beam containing the present invention 3 or 4 is consolidated
Change type resin combination.
The present invention 6 is a kind of cured film, and it irradiates by the hard paint of active energy ray curable described in the present invention 5
Active energy beam makes it solidify and obtain.
The present invention 7 is a kind of in-mold decoration film, its cured film for being laminated with the present invention 6.
The present invention 8 is a kind of injection-moulding plastic product, it uses the in-mold decoration film of the present invention 7.
Invention effect
The active energy beam resin provided by using the present invention and the hard paint using the resin, using the teaching of the invention it is possible to provide
Following decorating film, it is after active energy ray-curable, and cure shrinkage is small, and film ductility (degree of stretching) is high, and with it is existing
The equal hard painting propert of the hard paint of active energy ray curable, therefore, with：Add for the bending in injection moulding operation
Stress when work and drawing process is difficult to the good processability for cracking and with same with conventional widely used hard paint
Deng pencil hardness good hard painting propert, can it is relatively difficult to achieve so far not to complicated shape and deep-draw deep processing etc. into
The design of type product provides the surface for being difficult to scratch in the case of being any limitation as.Furthermore, it is possible to not damage the situation of optical characteristics
Under obtain the extremely low desciccator diaphragm of viscosity such that it is able to suppress the adhesion after being batched with the adhesion of the conveying roller of coating machine etc., reel,
Therefore, it is possible to provide good operability with high efficiency.Specific embodiment
Active energy ray curable resin of the invention, weight average molecular weight is 10000 ~ 100000, by making α, β-no
Saturated carboxylic acid (hereinafter referred to as (C) composition) is obtained with having the polymer reaction of branched structure as follows, and the polymer passes through
Make containing (methyl) acrylic ester monomer (hereinafter referred to as (A) composition) of epoxy radicals and (also referred to as single in any one end
End) there is the macromonomer (hereinafter referred to as (B) composition) without epoxy radicals of unsaturated double-bond with weight ratio (A):
(B) it is 80:20~40:60 are reacted and are obtained.
Above-mentioned (A) composition is that have at least one epoxy radicals and a compound for unsaturated double-bond in intramolecular.Specifically
For, can enumerate：(methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, 3,4- epoxide rings
Hexyl methyl (methyl) acrylate, 1- vinyl -3,4- 7-oxa-bicyclo[4.1.0s etc..Wherein, easiness and it is supplied in for obtaining
This consideration, preferably (methyl) glycidyl acrylate.
As above-mentioned (B) composition, as long as any one end there is unsaturated double-bond and do not contain epoxy radicals and
The macromonomer of the weight average molecular weight 1000 ~ 20000 of carboxyl, is not particularly limited, it is possible to use known compound.Such as
Fruit contains epoxy radicals, then in the addition reaction of (C) composition, also have in the same manner as main chain in side chain and pass through active-energy
The unsaturated double-bond group that radiation exposure is crosslinked, although hard painting propert is improved, but processability reduction.In addition, if be containing
The chemical constitution of carboxyl, then in α, in the addition reaction step of beta-unsaturated carboxylic acid, cause the epoxy radicals of main chain and the carboxylic of side chain
, there is gelation in the addition reaction of base.In addition, when weight average molecular weight is less than 1000, the pencil of the expression hard painting propert of cured film is hard
Degree is reduced, and when weight average molecular weight is more than 20000, the intermiscibility with (A) composition and organic solvent is deteriorated.
As the concrete example of above-mentioned (B) composition, can enumerate：The AA-6 of Toagosei Co., Ltd マ Network ロ モ ノ マ mono-,
Macromonomer that AB-6, AY-707S etc. are made up of the free-radical polymerized thing of the monomer with unsaturated double-bond, with intelligence rope strain formula
The macromolecular list being made up of the condensation product of dimethyl siloxane that commercial firm サ イ ラ プ レ mono- Application FM-0711, FM-0721 are enumerated
Body, with being made up of the ring-opening polymerization polymer of 6-caprolactone of enumerating of Daisel chemical industry Co., Ltd プ ラ Network セ Le FA10L
Macromonomer, with Japan Oil Co Block レ Application マ mono- PME-4000, PSE-1300 etc. enumerate by alcohols and epoxyalkane
The macromonomer etc. that constitutes of addition polymer.
The manufacture method of above-mentioned (B) composition, is not particularly limited, for example, can be by Japanese Unexamined Patent Publication 8-73577
The method synthesis proposed in publication, 1 No. 8 publications of Japanese Unexamined Patent Publication 2001-643.Specifically, in the mercaptan as chain-transferring agent
In the presence of, the copolyreaction of the monomer with unsaturated double-bond is carried out, synthesis at least introduces the copolymerization of hydroxyl in single end
After thing, make 2- methylacryoyloxyethyls isocyanates or methacrylic chloride etc. that addition reaction occur with hydroxyl, such that it is able to
Obtaining single end has the polymer of free-radical polymerized property group.Additionally, being proposed by Toagosei Co., Ltd river He Shi etc.
By the radical polymerization under high temperature without the macromonomer manufacture method (East Asia study on the synthesis year using chain-transferring agent etc.
Reported TREND2002 the 5th are p.2-10).By these, any one method can be manufactured.
As the monomer with unsaturated double-bond of the raw material of above-mentioned (B) composition, it is not particularly limited, specifically, can
To enumerate：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate,
(methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) acrylic acid-2-ethyl oneself
Ester, (methyl) decyl acrylate, (methyl) lauryl ester, (methyl) acrylic acid hexadecane ester, (methyl) acrylic acid ten
Eight alkyl esters, (methyl) acrylic acid -2- hydroxyl ethyl esters, (methyl) hydroxypropyl acrylate, (methyl) hy-droxybutyl, glycerine list (first
Base) acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, (methyl) acrylic acid ring
Own ester, (methyl) acrylic acid -4- t-butyl cyclohexyl methacrylates, N- acryloyl-oxyethyls hexahydrophthalic phthalimide, (methyl) third
Olefin(e) acid dicyclopentenyl ester, (methyl) benzyl acrylate, (methyl) acrylate, (methyl) isobornyl acrylate,
Polysiloxanes list (methyl) acrylate etc., styrene, it is possible to use a kind of, it is also possible to and with two or more.Wherein, from raw material
Cost and from the viewpoint of taking into account processability and hard painting propert, preferably (methyl) methyl acrylate, (methyl) isobutyl acrylate,
(methyl) tert-butyl acrylate, styrene.
It is preferred that above-mentioned (B) composition be with formula (1) represent end structure with free-radical polymerised free radical
Copolymer.
(in formula, X is the position with free-radical polymerised group, R1It is H or CH3, R2It is-C (=O) OR3Or phenyl, R3For
Selected from by-CH3、-CH2CH(CH3)2、-C(CH3)3And-(CH2)mCH3It is any in the group of (m represents 1 ~ 17 integer) composition
A kind of structure.N represents integer).Thus, condensation product with above-mentioned dimethyl siloxane, the ring-opening polymerization polymer of 6-caprolactone, alcohols
Compared with addition polymer with epoxyalkane etc., various of monomer can be selected as raw material, be easily controlled the physical property of cured film.This
Outward, in this case, by combining the two or more monomers with unsaturated double-bond as raw material, can more easily control solid
Change the physical property of film.
From make as the solidfied material of the active energy ray curable resin of final product take into account excellent processability with it is hard
Tu Xing, low viscosity, make excellent optical characteristics from the viewpoint of, the weight ratio preferably 80 of above-mentioned (A) composition and (B) composition:20~
40:60.By being set as the weight ratio, the operability of desciccator diaphragm and the physical property of cured film can be controlled.That is, the ratio of (A) composition
When example is too high, although hard painting propert is improved but processability and its tack, when the ratio of (B) composition is too high, although viscosity becomes good
And make the operability raising of desciccator diaphragm, but the hard painting propert of cured film is reduced.
The radical polymerization initiator used during as by above-mentioned (A) composition and (B) composition copolymerization, is not particularly limited,
Known radical polymerization initiator can be used.Specifically, can enumerate for example：Hydrogen peroxide, ammonium persulfate, persulfuric acid
The organic peroxides such as the inorganic peroxides such as potassium, benzoyl peroxide, cumyl peroxide, dilauroyl peroxide, 2,2 '-
Azo compounds such as azodiisobutyronitrile, 2,2 '-azo-bis-iso-dimethyl etc..These can be used alone one kind,
Can be used in mixed way two or more.It should be noted that it is preferred that making the usage amount of radical polymerization initiator relative to all poly-
100 weight portions of synthesis point are for about 0.01 weight portion ~ about 8 weight portions.It should be noted that as needed, it is also possible to turned using chain
Move agent etc..
As chain-transferring agent, can enumerate for example：Positive lauroyl mercaptan (n- ラ ウ リ Le メ Le カ プ タ Application), positive 12
Alkyl hydrosulfide, 2-mercaptobenzothiazole, bromine chloroform etc..These can be used alone one kind, it is also possible to be used in mixed way two kinds
More than.It is preferred that make the usage amount of chain-transferring agent relative to the weight portion of whole polymeric composition 100 for being used be for about 0.01 weight portion ~
About 5 weight portions.
(C) composition is reacted with the copolymer (A/B copolymers) of (B) composition with (A) composition for so obtaining, obtain activity
Energy ray-curable resin.As (C) composition, can be not particularly limited to use various known compounds.It is specific and
Speech, can enumerate the α such as (methyl) acrylic acid, β-unsaturated monocarboxylic, (methyl) acrylic acid dimer etc..Wherein, from resulting
The photopolymerization reaction of active energy ray curable resin and the hard painting propert of solidfied material from the viewpoint of, preferably (methyl)
Acrylic acid.
(C) composition is added after above-mentioned A/B copolymers occur open loop with the epoxy radicals that the reaction of (C) composition is (A) composition
Into reaction.On reaction method, it is not particularly limited, can be using known method.Generally, by by A/B copolymers with
(C) composition mixing, is heated to 80 ~ 120 DEG C of temperature to carry out in the presence of various catalyst as needed.
It is preferred that with the epoxy radix relative to above-mentioned A/B copolymers, carboxyl reach equal number of mode coordinate (C) into
Point.If carboxyl number is fewer than epoxy radix, produces the crosslinking between epoxy radicals and viscosify.In addition, (C) composition is generally to skin
Excitant is high.Therefore, when carboxyl number is excessively coordinated compared with epoxy radix, as not anti-in the presence of having in the product
The state of (C) composition for the carboxyl answered, it is not preferred from from the viewpoint of usability.
As above-mentioned catalyst, for example, as base catalyst, can enumerate：Pyridine, pyrroles, triethylamine, diethylamine,
The phosphines such as the amine such as dibutyl amine and ammonia, tributylphosphine, triphenylphosphine, as acid catalyst, can enumerate：Copper naphthenate, cycloalkanes
Lewis acid, the dibutyl such as metallic alkoxide compound, the aluminium chloride such as sour cobalt, zinc naphthenate, aluminium butoxide, four butoxy Tritanium/Trititaniums
Organo-tin compounds such as tin dilaurate etc..The usage amount of catalyst is not particularly limited, generally, relative to A/B copolymers
With the weight portion of total weight 100 of (C) composition, preferably from about 0.01 weight portion ~ about 5 weight portions.
In the reaction of above-mentioned A/B copolymers and (C) composition, as needed, it is also possible to use polymerization inhibitor.
As above-mentioned polymerization inhibitor, can enumerate：P methoxy phenol, hydroquinones, Trimethyl Hydroquinone, N- nitrosos
Phenylhydroxylamine etc..The usage amount of polymerization inhibitor is not particularly limited, in order to the reaction curability not to resulting resin is produced
Harmful effect, relative to the weight portion of total weight 100 of A/B copolymers and (C) composition, generally, it is preferred to for about 1 weight portion with
Under.In addition, in order to prevent polymerization, it is also possible to being blown into air etc. in reaction system.
As what is used in the reaction of the copolyreaction of (A) composition and (B) composition and A/B copolymers with (C) composition
Solvent, as long as dissolving the organic solvent of each composition, is not particularly limited, it is possible to use known solvent.Specifically, may be used
To enumerate：The alcohols such as propyl alcohol, butanol；The rudimentary ketone such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK)；The aromatic hydrocarbons such as toluene, benzene
Class；Butyl acetate, ethyl acetate, chloroform, dimethylformamide etc..These can be used alone one kind, it is also possible to be used in mixed way
It is two or more.In each reactions steps, if reaction temperature is set to higher, can efficiently carry out in a short time anti-
Should, it is therefore preferable that boiling point solvent high, but as the hard paint of active energy ray curable, if it is considered that it is preferred that drying property
The aspect of good hard paint, due to methyl iso-butyl ketone (MIBK), butyl acetate, can be set to reaction temperature higher, and dries
Property it is good, therefore preferably.
For the active energy ray curable resin of the invention for so obtaining, due to a high molecular polymer
(HMW body) is while have two positions, the unsaturated double-bond group for being irradiated by active energy beam and being crosslinked
Position and the side chain without bridging property reactive group position, therefore, it is possible to take into account hard painting propert and processability.And then, lead to
The side chain to form specific molecular weight is crossed, desciccator diaphragm surface can be made to be low viscosity.
The weight average molecular weight of the active energy ray curable resin of the invention for so obtaining is (using the polyphenyl second of GPC
Alkene scaled value) it is for about 10000 ~ 100000, can be used in the way of the mixed liquor containing organic solvent.Weight average molecular weight is less than
In the case of 10000, the tendency of the ductility reduction with cured film damages processability.On the other hand, the feelings more than 100000
Under condition, the intermiscibility with organic solvent is deteriorated, it is impossible to realize high-grade manufacture of stabilization.
The active-energy containing active energy ray-curable resin of the invention and Photoepolymerizationinitiater initiater can be obtained to penetrate
The hard paint of line curing type, this is also one of the present application.The also activity containing multifunctional (methyl) acrylate can be obtained
The hard paint of energy ray-curable, this is also one of the present application.By using multifunctional (methyl) acrylate, can adjust
Save the processability and hard painting propert of hard paint.Additionally, the hard paint of active energy ray curable of the invention can also coordinate addition
Agent.By coordinating additive, can obtain that the flatness of coating surface can be improved, assign the functions such as soil resistance and antistatic behaviour
The hard paint of property.
As above-mentioned additive, according to purpose can containing antioxidant, ultra-violet absorber, light stabilizer, defoamer,
Surface conditioner, antistain agent, pigment, antistatic additive, metal oxide microparticle dispersion etc..
5 ~ 80 weights in multifunctional (methyl) acrylate contained in hard paint of the invention, preferably resin composition
Measure the composition ratio of %.Thus, it is possible to used in the range of the hardness and ductility of cured film not departing from be taken into account.
As above-mentioned multifunctional (methyl) acrylate, can enumerate：Trimethylolpropane tris (methyl) acrylate, three
Hydroxymethyl-propane ethyoxyl three (methyl) acrylate, glycerine ethyoxyl three (methyl) acrylate, (first of glycerine propoxyl group three
Base) acrylate, ethoxylation isocyanuric acid three (methyl) acrylate, modified three-(2- (methyl) acryloyl-oxy of 6-caprolactone
Ethyl) isocyanuric acid ester, pentaerythrite three/tetra- (methyl) acrylate, pentaerythrite ethyoxyl three/tetra- (methyl) acrylic acid
Ester, pentaerythrite propoxyl group three/tetra- (methyl) acrylate, two trimethylolpropane four (methyl) acrylate, two seasons penta 4
The acrylic monomers (1) such as modified dipentaerythritol six (methyl) acrylate of alcohol six (methyl) acrylate, 6-caprolactone, pass through
Polyhydric isocyanate compound and carbamate (first obtained from the reaction of (methyl) acrylate compounds containing hydroxyl
Base) acrylate (2), make multicomponent isocyanate with containing two or more hydroxyl compound reaction obtained from containing end it is different
The compound of cyanic acid ester group again with carbamate (methyl) acrylic acid obtained from (methyl) acrylate reactions of hydroxyl
Ester (2) ', make (methyl) acrylic acid epoxy ester (3) obtained from (methyl) acrylic acid and epoxy radicals addition.Preferably carbamic acid
Ester (methyl) acrylate (2) and (2) ', (methyl) acrylic acid epoxy ester (3).It should be noted that these can be each independent
Use, it is also possible to and it is two or more with coordinating.Using it is two or more when each multifunctional (methyl) acrylate component use
Ratio, is not particularly limited.
In order to improve wear resistance, hard paint of the invention can coordinate with inorganic filler.As inorganic filler, can
The known inorganic fillers such as silica or metal oxide microparticle are used with without restriction.Can enumerate for example：Oxidation
Titanium, aluminum oxide, antimony oxide, tin oxide, zirconium oxide, zinc oxide, cerium oxide, indium oxide etc..These can be used alone one kind,
Can be applied in combination two or more.Wherein, commercially product is abundant, be readily available, cheap aspect is set out, preferably dioxy
SiClx, titanium oxide, aluminum oxide, zirconium oxide and zinc oxide.
Preferably use and the average grain diameter of above-mentioned inorganic filler is controlled into 200nm (using laser diffraction and scattering method) below
Filler.When average grain diameter is more than 200nm, albefaction is susceptible in cured film, it is possible to damage mist degree and efficiency of transmission
Etc. optical characteristics.And, the various additives such as levelling agent, defoamer, slip agent, sensitising agent can also be coordinated as needed.
In the case where solidifying hard paint of the invention with ultraviolet, it is possible to use Photoepolymerizationinitiater initiater.It is poly- as light
Initiator is closed, as long as the material decomposed by ultraviolet, produce free radical and trigger polymerization, is not particularly limited,
Known compound can be used.Specifically, can enumerate for example：2,2- dimethoxy -1,2- diphenylethane -1- ketone,
1- cyclohexyl-phenyl ketones, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 1- [4- (2- hydroxyl-oxethyls)-phenyl] -2- hydroxyls
Base -2- methyl isophthalic acids-propane -1- ketone, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholino propane -1- ketone, 2- benzyls -2- two
Methylamino -1- (4- morphlinophenyls)-butanone -1, double (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides, 2,4,6- tri-
Methyl benzoyl-diphenyl-phosphineoxide, 4- methyl benzophenones etc., can easily obtain from Qi Ba Amada Co., Ltd.s etc.
.These can be used alone one kind, it is also possible to be applied in combination two or more.It is preferred that making the usage amount of Photoepolymerizationinitiater initiater relative
In the weight portion of active energy ray-curable resin composition 100 be for about 0.1 weight portion ~ about 10 weight portions.
Additionally, being obtained by solidifying it hard paint irradiation active energy beam of above-mentioned active energy ray curable
Cured film be also one of present invention.If using cured film of the invention, could be as would taking into account processability and hard painting propert
Decorating film is used.
As above-mentioned active energy beam, light (light such as ultraviolet), electron ray, X-ray, alpha ray, β can be enumerated
Ray, gamma-rays, neutron ray etc..Generally from widely available aspect, be used in combination for light and electron ray by recommendation.
The decorating film for being laminated with above-mentioned cured film is also one of present invention.The in-mold decoration film is for so far because of hard conating
Crackle and the deep design of the shape that cannot be applicable also is coped with, the surface of products formed can be assigned and be difficult to in the past equal
The hard painting propert of scuffing.As method, as long as carrying out film laminating and injection molding method simultaneously in mould, then can not have
Adapt to being particularly limited to, specifically, can be used in in-mold decoration, in-mold labels, in-molded, film insert molding etc..
As the base material of above-mentioned decorating film, it is not particularly limited, can enumerates for example：Plastics (makrolon, poly- methyl-prop
E pioic acid methyl ester, polystyrene, polyester, polyolefin, epoxy resin, melmac, tri acetyl cellulose resin, ABS trees
Fat, AS resins, norbornene resin etc.).
As the method for the stacking hard conating on above-mentioned decorating film, can be coated with by known method, after drying, irradiation
Active energy beam, solidifies it, thus carries out.As the coating method of hard paint, can enumerate for example：Scrape rod coating, silk
Rod coating (the バ mono- Tu works of メ イ ヤ mono-), airblade coating, intaglio plate coating, reverse intaglio plate coating, hectographic printing, flexographic printing, silk
Version printing method etc..It should be noted that coating weight is not particularly limited, generally, dried weight is in 0.1 ~ 20g/m2, preferably
0.5~10g/m2Scope.
The present invention is also the injection-moulding plastic product for using above-mentioned decorating film.In the past, due to hard conating crackle problem,
Therefore, force the hard painting propert of injection-moulding plastic product to give way, or there is system in design and limit, but if using this hair
Bright decorating film, then can obtain the design of correspondence complexity and be difficult to the injection-moulding plastic product for scratching on the surface, can
Made with the part in the housing of the electronic product such as mobile phone terminal and PC, in-car interior trim panel and extraneous adornment cover
With.
Embodiment
Hereinafter, embodiment and comparative example are enumerated, the present invention is specifically illustrated, but the invention is not restricted to these examples
Son.It should be noted that in each example, part and % unless otherwise specified, then all weight basis.
<(B) synthesis example 1 of composition>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
9.5 parts of methyl methacrylates (below, MMA), 0.8 part of mercaptopropionic acid, 48.1 parts of butyl acetates, 0.5 part of azo two of input are different
Butyronitrile (below, AIBN) is simultaneously stirred, and after 90 DEG C are warming up under stream of nitrogen gas, has 38.0 parts of MMA, 1.5 from input in advance
The dropping funel of part AIBN was added dropwise with 2 hours, and 5 hours are incubated at 90 DEG C.Then, 0.5 part of AIBN is put into, insulation 1 is small
Shi Hou, is warming up to 120 DEG C, after being incubated 2 hours, is cooled to normal temperature, and 1.1 parts of GMAs of input are (below,
GMA), 0.3 part of triphenylphosphine, 0.1 part of p methoxy phenol, unloads dropping funel, and nitrogen influx is substituted for into air bubbling
Device, is stirred while air is blasted, and is warming up to 110 DEG C, is incubated 9 hours, and thus, it is 50% to obtain solid constituent
Contain the MMA macromonomer solution of methylacryloyl in single end.It should be noted that weight average molecular weight is (using the poly- of GPC
Styrene scaled value) it is 4600.Weight average molecular weight is represented gel permeation chromatograph (TOSOH Co., Ltd's system, trade name " HLC-
8220 ", chromatographic column：TOSOH Co., Ltd's system, trade name " TSKgel superHZ2000 ") be connected in series two and determine
Value.
<(B) synthesis example 2 of composition>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
11.8 parts of MMA of input, 0.2 part of 2 mercapto ethanol, 39.7 parts of butyl acetates, 0.5 part of AIBN are simultaneously stirred, under stream of nitrogen gas
After being warming up to 90 DEG C, it was added dropwise with 2 hours from the dropping funel that has 47.3 parts of MMA, 0.4 part of AIBN is in advance put into, at 90 DEG C
After insulation 5 hours, the AIBN of 0.5 part of input after being incubated 1 hour, is warming up to 120 DEG C, is incubated 2 hours.It is then cooled to often
Temperature, puts into 0.4 part of acrylic acid 2- isocyano groups ethyl ester, 0.03 part of stannous octoate, 0.1 part of p methoxy phenol, 6 is incubated at 80 DEG C small
When, thus, obtain the MMA macromonomer solution that methylacryloyl is contained in single end that solid constituent is 60%.Need explanation
, weight average molecular weight (using the polystyrene conversion value of GPC) is 22000.
<(B) synthesis example 3 of composition>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
8.1 parts of MMA of input, 6.3 parts of 2 mercapto ethanols, 49.7 parts of butyl acetates, 0.1 part of AIBN are simultaneously stirred, under stream of nitrogen gas
After being warming up to 90 DEG C, it was added dropwise with 2 hours from the dropping funel that has 24.1 parts of MMA, 0.3 part of AIBN is in advance put into, at 90 DEG C
After insulation 5 hours, the AIBN of 0.5 part of input after being incubated 1 hour, is warming up to 120 DEG C, is incubated 2 hours.It is then cooled to often
Temperature, puts into 11.3 parts of acrylic acid 2- isocyano groups ethyl esters, 0.02 part of stannous octoate, 0.1 part of p methoxy phenol, and 6 are incubated at 80 DEG C
Hour, thus, obtain the MMA macromonomer solution that methylacryloyl is contained in single end that solid constituent is 50%.Need
Illustrate, weight average molecular weight (using the polystyrene conversion value of GPC) is 700.
<Embodiment 1>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
3.3 parts of GMA, the MMA macromonomers of 9.8 parts of synthesis examples 1 as (B) composition, 13.1 parts of methyl as (A) composition of input
Isobutyl ketone (below, MIBK) and 0.3 part of AIBN are simultaneously stirred, after 110 DEG C are warming up under stream of nitrogen gas, from advance
Input has and dissolves 1.0 parts of drops of the mixed liquor of AIBN in 9.8 parts of GMA, the MMA macromonomers of 29.5 parts of synthesis examples 1
Liquid funnel was added dropwise with 2 hours, then, after making its reaction 5 hours, added 0.2 part of AIBN, then was incubated 1 hour, was warming up to
116 DEG C, 3 hours are incubated, thus, obtain weight ratio (A):(B)=40:60 copolymer with branched structure.Then, cool down
To normal temperature, acrylic acid (have epoxy radix equal number of carboxyl) with copolymer of 6.7 parts of the input as (C) composition,
0.3 part of triphenylphosphine, 0.1 part of p methoxy phenol, 26.2 parts of MIBK, unload dropping funel, and nitrogen influx is substituted for into sky
Enraged bulb apparatus, are stirred while air is blasted, and are reacted 6 hours at 110 DEG C, thus, obtain with branched structure
Active energy ray curable resin.Weight average molecular weight (using the polystyrene conversion value of GPC) is that 32000, solid constituent is
40%.To cooperation Photoepolymerizationinitiater initiater (trade name " イ Le ガ キ ユ ア 184 " BASF) 2 in 100 parts resulting of resin solution
Part, obtain hard paint.
<Embodiment 2>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
3.9 parts of GMA as (A) composition of input, the MMA macromonomers of 7.9 parts of synthesis examples 1 as (B) composition, 15.7 parts
MIBK and 0.3 part of AIBN is simultaneously stirred, and after 110 DEG C are warming up under stream of nitrogen gas, has at 11.8 parts from input in advance
1.0 parts of dropping funels of the mixed liquor of AIBN are dissolved in GMA, the MMA macromonomers of 23.6 parts of synthesis examples 1 with 2 hours
It is added dropwise, then, after making its reaction 5 hours, is added 0.2 part of AIBN, then be incubated 1 hour, be warming up to 116 DEG C, insulation 3 is small
When, thus, obtain weight ratio (A):(B)=50:50 copolymer with branched structure.It is then cooled to after normal temperature, input
8.0 parts of acrylic acid (there is the equal number of carboxyl of epoxy radix with copolymer), 0.2 part of triphenyl as (C) composition
Phosphine, 0.1 part of p methoxy phenol, 27.5 parts of MIBK, unload dropping funel, and nitrogen influx is substituted for into air bubbling device,
It is stirred while air is blasted, is reacted 6 hours at 110 DEG C, obtains the active energy ray-curable with branched structure
Type resin.Weight average molecular weight (using the polystyrene conversion value of GPC) is 28000, and solid constituent is 40%.To resulting tree
Coordinate 2 parts of イ Le ガ キ ユ ア 184 in 100 parts of lipoprotein solution, obtain hard paint.
<Embodiment 3>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
5.1 parts of GMA as (A) composition of input, the MMA macromonomers of 4.4 parts of synthesis examples 1 as (B) composition, 20.4 parts
MIBK and 0.3 part of AIBN is simultaneously stirred, and after 110 DEG C are warming up under stream of nitrogen gas, has at 15.3 parts from input in advance
0.9 part of dropping funel of the mixed liquor of AIBN is dissolved in GMA, the MMA macromonomers of 13.1 parts of synthesis examples 1 with 2 hours
It is added dropwise, then, after making its reaction 5 hours, is added 0.2 part of AIBN, then be incubated 1 hour, be warming up to 116 DEG C, insulation 3 is small
When, thus, obtain weight ratio (A):(B)=70:30 copolymer with branched structure.It is then cooled to after normal temperature, input
10.4 parts of acrylic acid (there is the equal number of carboxyl of epoxy radix with copolymer), 0.3 part of triphenyl as (C) composition
Phosphine, 0.1 part of p methoxy phenol, 29.8 parts of MIBK, unload dropping funel, and nitrogen influx is substituted for into air bubbling device,
It is stirred while air is blasted, is reacted 6 hours at 110 DEG C, obtains the active energy ray-curable with branched structure
Type resin.Weight average molecular weight (using the polystyrene conversion value of GPC) is 14000, and solid constituent is 40%.To resulting tree
Coordinate 2 parts of イ Le ガ キ ユ ア 184 in 100 parts of lipoprotein solution, obtain hard paint.
<Embodiment 4>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
4.0 parts of GMA as (A) composition of input, the MMA macromonomers of 7.9 parts of synthesis examples 1 as (B) composition, 15.8 parts
MIBK and 0.2 part of AIBN is simultaneously stirred, and after 80 DEG C are warming up under stream of nitrogen gas, has at 11.9 parts from input in advance
0.5 part of dropping funel of the mixed liquor of AIBN is dissolved in GMA, the MMA macromonomers of 23.8 parts of synthesis examples 1 with 2 hours
It is added dropwise, then, after making its reaction 5 hours, is added 0.1 part of AIBN, then be incubated 1 hour, be warming up to 116 DEG C, insulation 3 is small
When, thus, obtain weight ratio (A):(B)=50:50 copolymer with branched structure.It is then cooled to after normal temperature, input
8.0 parts of acrylic acid (have the equal number of carboxyl of epoxy radix) with copolymer as (C) composition, 0.3 part of triphenylphosphine,
0.1 part of p methoxy phenol, 27.7 parts of MIBK, unload dropping funel, nitrogen influx are substituted for into air bubbling device, in drum
It is stirred while entering air, is reacted 6 hours at 110 DEG C, obtains the active energy ray curable tree with branched structure
Fat.Weight average molecular weight (using the polystyrene conversion value of GPC) is 85000, and solid constituent is 40%.It is molten to resulting resin
Coordinate 2 parts of イ Le ガ キ ユ ア 184 in 100 parts of liquid, obtain hard paint.
<Embodiment 5>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
3.9 parts of GMA, 3.9 parts of styrene macromer (trade name " AS-6 " East Asia as (B) composition as (A) composition of input
Synthesis Co., Ltd.), 15.7 parts of MIBK and 0.3 part of AIBN and be stirred, have molten in 15.7 parts of MIBK from input in advance
11.8 parts of AS-6 of solution, the dropping funel of the mixed liquor of 1.0 parts of AIBN were added dropwise with 2 hours, then, made its reaction 5 small
Shi Hou, adds 0.2 part of AIBN, then is incubated 1 hour, is warming up to 116 DEG C, is incubated 3 hours, thus, obtains weight ratio (A):(B)=
50:50 copolymer with branched structure.It is then cooled to after normal temperature, acrylic acid (tool of 8.0 parts of the input as (C) composition
Have the equal number of carboxyl of epoxy radix with copolymer), 0.3 part of triphenylphosphine, 0.1 part of p methoxy phenol, 27.3 parts
MIBK, unloads dropping funel, and nitrogen influx is substituted for into air bubbling device, is stirred while air is blasted, 110
Reacted 6 hours at DEG C, obtain the active energy ray curable resin with branched structure.Weight average molecular weight is (using the poly- of GPC
Styrene scaled value) it is 24000, solid constituent is 40%.To 2 parts of イ Le ガ キ ユ of cooperation in 100 parts resulting of resin solution
ア 184, obtains hard paint.
<Embodiment 6>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
3.9 parts of GMA, 8.0 parts of Isobutyl methacrylate macromonomer (trade names as (B) composition as (A) composition of input
" AW-6S " Toagosei Co., Ltd), 22.5 parts of MIBK and 0.3 part of AIBN be stirred, be warming up under stream of nitrogen gas
After 110 DEG C, there are 1.0 parts of dropping liquids of the mixed liquor of AIBN of dissolving in 11.8 parts of GMA, 24.0 parts of AW-6S from input in advance
Funnel was added dropwise with 2 hours, then, after making its reaction 5 hours, added 0.2 part of AIBN, then was incubated 1 hour, was warming up to 116
DEG C, 3 hours are incubated, thus, obtain weight ratio (A):(B)=50:50 copolymer with branched structure.It is then cooled to often
Wen Hou, acrylic acid (have epoxy radix equal number of carboxyl) with copolymer of 8.0 parts of the input as (C) composition, 0.2 part
Triphenylphosphine, 0.1 part of p methoxy phenol, 20.5 parts of MIBK, unload dropping funel, and nitrogen influx is substituted for into air bubbling
Device, is stirred while air is blasted, and is reacted 6 hours at 110 DEG C, obtains the active energy beam with branched structure
Gel-type resin.Weight average molecular weight (using the polystyrene conversion value of GPC) is 26000, and solid constituent is 40%.To resulting
100 parts of resin solution in coordinate 2 parts of イ Le ガ キ ユ ア 184, obtain hard paint.
<Embodiment 7>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
15.1 parts of MIBK of input are simultaneously stirred, while after 90 DEG C are warming up under stream of nitrogen gas, being added dropwise from dropping funel with 2 hours pre-
It is first Toagosei Co., Ltd in 18.1 parts of GMA as (A) composition, 12.0 parts of MMA macromonomers as (B) composition
The mixed solution of 15.1 parts of MIBK of dissolving in trade name " AA-6 ", 1.2 parts of AIBN, then, after making its reaction 5 hours, plus
Enter 0.6 part of AIBN, then be incubated 1 hour, be warming up to 116 DEG C, be incubated 3 hours, thus, obtain weight ratio (A):(B)=60:40
Copolymer.It is then cooled to after normal temperature, acrylic acid of 9.2 parts of the input as (C) composition (has the epoxy radix with copolymer
Equal number of carboxyl), 0.3 part of triphenylphosphine, 0.1 part of p methoxy phenol, 28.4 parts of MIBK, dropping funel is unloaded, by nitrogen
Air flow inlet is substituted for air bubbling device, is stirred while air is blasted, and is reacted 6 hours at 110 DEG C, thus, obtains
To active energy ray curable resin.Weight average molecular weight is 18000, and solid constituent is 40%.To resulting resin solution
Coordinate 2 parts of イ Le ガ キ ユ ア 184 in 100 parts, obtain hard paint.
<Comparative example 1>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
6.6 parts of GMA, 26.2 parts of MIBK and 0.3 part of AIBN of input are simultaneously stirred, after 110 DEG C are warming up under stream of nitrogen gas, from
Input has 0.8 part of dropping funel of the mixed liquor of AIBN of dissolving in 19.7 parts of GMA to be added dropwise with 2 hours in advance, so
Afterwards, after making its reaction 5 hours, 0.1 part of AIBN is added, then is incubated 1 hour, be warming up to 116 DEG C, be incubated 3 hours, thus, obtained
GMA homopolymers.It is then cooled to after normal temperature, 13.3 parts of acrylic acid of input (have equal number of with the epoxy radix of copolymer
Carboxyl), 0.3 part of triphenylphosphine, 0.1 part of p methoxy phenol, 32.7 parts of MIBK, unload dropping funel, nitrogen influx is replaced
Change air bubbling device into, be stirred while air is blasted, reacted 6 hours at 110 DEG C, obtain acrylic acid epoxy ester.
Weight average molecular weight (using the polystyrene conversion value of GPC) is 20000, and solid constituent is 40%.To resulting resin solution
Coordinate 2 parts of イ Le ガ キ ユ ア 184 in 100 parts, obtain hard paint.
<Comparative example 2>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
3.9 parts of GMA of input, 3.9 parts of MMA, 31.5 parts of MIBK and 0.3 part of AIBN are simultaneously stirred, and are warming up under stream of nitrogen gas
After 110 DEG C, there is the dropping liquid leakage that 0.9 portion of mixed liquor of AIBN is dissolved in 11.8 parts of GMA, 11.8 parts of MMA from input in advance
Bucket was added dropwise with 2 hours, then, after making its reaction 5 hours, added 0.2 part of AIBN, then was incubated 1 hour, was warming up to 116 DEG C,
Insulation 3 hours, thus, obtains GMA/MMA copolymers.It is then cooled to after normal temperature, 8.0 parts of acrylic acid of input (have and GMA/
The equal number of carboxyl of epoxy radix of MMA copolymers), 0.3 part of triphenylphosphine, 0.1 part of p methoxy phenol, 27.3 parts
MIBK, unloads dropping funel, and nitrogen influx is substituted for into air bubbling device, is stirred while air is blasted, 110
Reacted 6 hours at DEG C, obtain active energy ray curable resin.Weight average molecular weight (using the polystyrene conversion value of GPC)
It is 15000, solid constituent is 40%.To 2 parts of イ Le ガ キ ユ ア 184 are coordinated in 100 parts resulting of resin solution, obtain hard
Paint.
<Comparative example 3>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
3.9 parts of GMA as (A) composition of input, the MMA macromonomers of 6.6 parts of synthesis examples 2 as (B) composition, 15.7 parts
MIBK and 0.3 part of AIBN is simultaneously stirred, and after 110 DEG C are warming up under stream of nitrogen gas, has at 11.8 parts from input in advance
1.0 parts of dropping funels of the mixed liquor of AIBN are dissolved in GMA, the MMA macromonomers of 19.6 parts of synthesis examples 2 with 2 hours
It is added dropwise, then, after making its reaction 5 hours, is added 0.2 part of AIBN, then be incubated 1 hour, be warming up to 116 DEG C, insulation 3 is small
When, thus, obtain weight ratio (A):(B)=50:50 copolymer with branched structure.It is then cooled to after normal temperature, input
8.0 parts of acrylic acid (have the equal number of carboxyl of epoxy radix) with copolymer as (C) composition, 0.2 part of triphenylphosphine,
0.1 part of p methoxy phenol, 32.7 parts of MIBK, unload dropping funel, nitrogen influx are substituted for into air bubbling device, in drum
It is stirred while entering air, is reacted 6 hours at 110 DEG C, obtains the active energy ray curable tree with branched structure
Fat.Weight average molecular weight (using the polystyrene conversion value of GPC) is 52000, and solid constituent is 40%.It is molten to resulting resin
Coordinate 2 parts of イ Le ガ キ ユ ア 184 in 100 parts of liquid, obtain hard paint.
<Comparative example 4>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
3.9 parts of GMA as (A) composition of input, the MMA macromonomers of 7.9 parts of synthesis examples 3 as (B) composition, 15.7 parts
MIBK and 0.3 part of AIBN is simultaneously stirred, and after 110 DEG C are warming up under stream of nitrogen gas, has at 11.8 parts from input in advance
1.0 parts of dropping funels of the mixed liquor of AIBN are dissolved in GMA, the MMA macromonomers of 23.6 parts of synthesis examples 3 with 2 hours
It is added dropwise, then, after making its reaction 5 hours, is added 0.2 part of AIBN, then be incubated 1 hour, be warming up to 116 DEG C, insulation 3 is small
When, thus, obtain weight ratio (A):(B)=50:50 copolymer with branched structure.It is then cooled to after normal temperature, input
8.0 parts of acrylic acid (have the equal number of carboxyl of epoxy radix) with copolymer as (C) composition, 0.2 part of triphenylphosphine,
0.1 part of p methoxy phenol, 27.5 parts of MIBK, unload dropping funel, nitrogen influx are substituted for into air bubbling device, in drum
It is stirred while entering air, is reacted 6 hours at 110 DEG C, obtains the active energy ray curable tree with branched structure
Fat.Weight average molecular weight (using the polystyrene conversion value of GPC) is 18000, and solid constituent is 40%.It is molten to resulting resin
Coordinate 2 parts of イ Le ガ キ ユ ア 184 in 100 parts of liquid, obtain hard paint.
<Comparative example 5>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
4.0 parts of GMA as (A) composition of input, the MMA macromonomers of 8.0 parts of synthesis examples 1 as (B) composition, 15.9 parts
MIBK and 0.04 part of AIBN is simultaneously stirred, and after 110 DEG C are warming up under stream of nitrogen gas, has at 11.9 parts from input in advance
0.1 part of dropping funel of the mixed liquor of AIBN is dissolved in GMA, the MMA macromonomers of 23.8 parts of synthesis examples 1 with 2 hours
It is added dropwise, then, after making its reaction 5 hours, is added 0.1 part of AIBN, then be incubated 1 hour, be warming up to 116 DEG C, insulation 3 is small
When, thus, obtain weight ratio (A):(B)=50:50 copolymer with branched structure.It is then cooled to after normal temperature, input
8.1 parts of acrylic acid (have the equal number of carboxyl of epoxy radix) with copolymer as (C) composition, 0.2 part of triphenylphosphine,
0.1 part of p methoxy phenol, 27.7 parts of MIBK, unload dropping funel, nitrogen influx are substituted for into air bubbling device, in drum
It is stirred while entering air, is warming up to 110 DEG C and starts insulation, as a result gelation occurs after 1h.
<Comparative example 6>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
5.0 parts of GMA as (A) composition of input, the MMA macromonomers of 4.3 parts of synthesis examples 1 as (B) composition, 0.04 part it is just pungent
Base mercaptan, 20.0 parts of MIBK and 0.7 part of AIBN are simultaneously stirred, after 116 DEG C are warming up under stream of nitrogen gas, from throwing in advance
Enter to have to be dissolved in 14.9 parts of GMA, MMA macromonomers, 0.1 part of n octylmercaptan of 12.8 parts of synthesis examples 1 2.2 parts of AIBN and
Into the dropping funel of mixed liquor be added dropwise with 2 hours, then, after making its reaction 5 hours, add 0.4 part of AIBN, then be incubated
4 hours, thus, obtain weight ratio (A):(B)=70:30 copolymer with branched structure.It is then cooled to after normal temperature, throw
Enter 10.2 parts of acrylic acid (there is the equal number of carboxyl of epoxy radix with copolymer), 0.2 part of triphenyl as (C) composition
Phosphine, 0.1 part of p methoxy phenol, 29.2 parts of MIBK, unload dropping funel, and nitrogen influx is substituted for into air bubbling device,
It is stirred while air is blasted, is reacted 6 hours at 110 DEG C, obtains the active energy ray-curable with branched structure
Type resin.Weight average molecular weight (using the polystyrene conversion value of GPC) is 8000, and solid constituent is 40%.To resulting resin
Coordinate 2 parts of イ Le ガ キ ユ ア 184 in 100 parts of solution, obtain hard paint.
<Comparative example 7>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
27.2 parts of MIBK of input are simultaneously stirred, while after 90 DEG C are warming up under stream of nitrogen gas, being added dropwise from dropping funel with 2 hours pre-
It is first molten in 10.2 parts of GMA, 47.6 parts of MMA macromonomers obtained as the synthesis example 1 of (B) composition as (A) composition
1.4 parts of mixed solutions of AIBN of solution, then, after making its reaction 5 hours, add 0.6 part of AIBN, then are incubated 1 hour, heat up
To 116 DEG C, 3 hours are incubated, thus, obtain weight ratio (A):(B)=30:70 copolymer.It is then cooled to after normal temperature, input
5.2 parts of acrylic acid (have the equal number of carboxyl of epoxy radix) with copolymer as (C) composition, 0.2 part of triphenylphosphine,
0.1 part of p methoxy phenol, 7.6 parts of MIBK, unload dropping funel, nitrogen influx are substituted for into air bubbling device, in drum
It is stirred while entering air, is reacted 6 hours at 110 DEG C, thus, obtains the active energy ray-curable with branched structure
Type resin.Weight average molecular weight is 30000, and solid constituent is 40%.
<Comparative example 8>
In the four-hole boiling flask of mixer, thermometer, backflow cooler, nitrogen influx and dropping funel is installed,
4.4 parts of GMA as (A) composition of input, the MMA macromonomers of 1 part of synthesis example 1 as (B) composition, 27.5 parts of MIBK,
And 0.2 part of AIBN and be stirred, after 110 DEG C are warming up under stream of nitrogen gas, there are dissolving 13.3 parts of GMA, 3 from input in advance
The MMA macromonomers of part synthesis example 1, the dropping funel of the mixed liquor of 0.6 part of AIBN were added dropwise with 2 hours, then,
After making its reaction 5 hours, 0.1 part of AIBN is added, then be incubated 1 hour, be warming up to 116 DEG C, be incubated 3 hours, thus, obtain weight
Than (A):(B)=90:10 copolymer with branched structure.It is then cooled to after normal temperature, 20 parts of input is used as (C) composition
Acrylic acid (have the equal number of carboxyl of epoxy radix) with copolymer, 0.3 part of triphenylphosphine, 0.1 part of p methoxy phenol,
29.6 parts of MIBK, unload dropping funel, and nitrogen influx is substituted for into air bubbling device, are stirred while air is blasted
Mix, reacted 6 hours at 110 DEG C, obtain the active energy ray curable resin with branched structure.Weight average molecular weight (is utilized
The polystyrene conversion value of GPC) it is 10000, solid constituent is 40%.To 2 parts of イ of cooperation in 100 parts resulting of resin solution
Le ガ キ ユ ア 184, obtain hard paint.
<The regulation of hard paint>
Coordinate 50 parts of the hard paint obtained in 50 parts of hard paint, the comparative example 1 obtained in embodiment 2, will be by with side chain
The hard paint of active energy ray curable resin and the acrylic acid epoxy ester composition of structure is used as embodiment 8.
Table 1
(making 1 of evaluation film)
By the hard paint of each embodiment and comparative example 188 μm of thickness the easily gluing treatment poly terephthalic acid second of one side
It is coated with metering bar coater No.12 on the easy gluing surface of diol ester film (trade name " A4100 " Toyo Boseki K.K),
Dried 1 minute at 80 DEG C, remove solvent composition, make the dry coating of about 5 μm of thickness, viscosity is evaluated.
(evaluation of viscosity)
As the index of resistance to adhesive, viscosity is evaluated, carry out experiment as follows.By the making 1 of evaluation film
Dry coating cuts into the size of 5 × 5cm, and the polyethylene terephthalate film that will not carry out easy gluing treatment is fitted to
Face side is dried, is clamped in glass plate, apply 100g/cm2Load, 24 hours are stood, according to desciccator diaphragm with poly- to benzene
The adhesion situation of naphthalate film, is evaluated viscosity with 4 stages as follows.
4；The state not adhered to completely
3；With the position without adhesion, also it is easily peeled off at the position of adhesion
2；Although overall adhesion, is easily peeled off
1；Overall adhesion, it is difficult to peel off
3 will be evaluated and be judged as low viscosity, 4 will evaluated and be judged as more excellent low viscosity, the evaluation on evaluating more than 3,
It is considered as with resistance to adhesive.On the other hand, it may be said that it is the high state of viscosity to evaluate 2 for viscosity is poor, evaluate 1, will evaluation 2 with
Under evaluation be considered as without resistance to adhesive.
(making 2 of evaluation film)
To the dry coating of the making 1 of evaluation film, by high voltage mercury lamp radiation 300mJ/cm2Accumulated light, system
Make cured film, on Physical properties of coating film as shown below, evaluated.
For the cured film that the hard paint using each embodiment and comparative example makes, with following project, evaluation method
The experiment of hard painting propert and processability is carried out, table 2 is shown the result in.
(evaluation of hard painting propert)
Evaluation on hard painting propert, carries out the pencil hardness test of the test method based on JIS-K-5600, is evaluated.
Here, it is substantially poor that pencil hardness F is evaluated as into hard painting propert, pencil hardness H is evaluated as with hard painting propert, pencil hardness 2H is commented
Valency is with excellent hard painting propert.
(evaluation of processability)
Processability is evaluated with the ductility of cured film.Refer to for this in injection moulding if ductility is big
The stress of extension can be followed flexibly such that it is able to suppress the rupture of hard conating.
On ductility, cured film is cut into the test film of length 100mm, the strip of width 7mm with chuck spacing
50mm is installed on cupping machine (model " RTC-1250A " Co., Ltd. オ リ エ Application テ Star Network), in 25 DEG C of room temperature, humidity 45%
In the environment of RH, implemented with draw speed 10mm/ minutes, (prolonged chuck spacing respectively 55mm (ductility 10%), 60mm is made
Degree of stretching 20%), the point of 65mm (ductility 30%) stop, visually observation cured film has flawless, if without crackle, be evaluated as
Zero, if cracked, be evaluated as ×.
(measure of mist degree)
Active energy ray curable resin of the invention, requires the transparency after hardening.If the transparency is insufficient,
Damage the color as the design decorative pattern of the decorative pattern ink of substrate etc..The transparency on cured film, uses haze meter " HM-
150 " (color technical research institute in village), based on JIS-K-7105, the cured film made in the making 2 of evaluation of measuring film.
Measured value is less than 0.7, is evaluated as damaging the design of substrate, is set to "○", for more than 0.7, is judged as infringement design
The level of property, is set to "×".
Table 2
Claims (7)
1. a kind of active energy ray curable resin, it is characterised in that weight average molecular weight is 10000~100000, by making
α, beta-unsaturated carboxylic acid (C) is obtained with having the copolymer reaction of branched structure as follows, and the copolymer is by making containing epoxy
(methyl) acrylic ester monomer (A) of base and any one end there is unsaturated double-bond and do not contain epoxy radicals and
The macromonomer (B) of the weight average molecular weight 1000~20000 of carboxyl is with weight ratio (A):(B) it is 80:20~40:60 are carried out instead
Answer and obtain,
The macromonomer (B) is the freedom with free-radical polymerised group of the end structure represented with formula (1)
Base co-polymer,
In formula, X is the position with free-radical polymerised group, R1It is H or CH3, R2It is-C (=O) OR3Or phenyl, R3Be selected from
By-CH3、-CH2CH(CH3)2、-C(CH3)3And-(CH2)mCH3Any one structure in the group of composition, n represents integer, m tables
Show 1~17 integer.
2. a kind of active energy ray-curable resin composition, it is characterised in that contain：Active energy described in claim 1
Amount ray curing resin and Photoepolymerizationinitiater initiater.
3. active energy ray-curable resin composition as claimed in claim 2, wherein, also contain multifunctional (methyl) third
Olefin(e) acid ester.
4. a kind of hard paint of active energy ray curable, contains the active energy ray curable tree described in Claims 2 or 3
Oil/fat composition.
5. a kind of cured film, it is characterised in that it shines by the hard paint of active energy ray curable described in claim 4
Penetrating active energy beam makes it solidify and obtain.
6. a kind of decorating film, it is laminated with the cured film described in claim 5.
7. a kind of injection-moulding plastic product, it use the decorating film described in claim 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-241777 | 2011-11-03 | ||
| JP2011241777 | 2011-11-03 |
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| JP (1) | JP6048804B2 (en) |
| KR (1) | KR20130049154A (en) |
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| JP2015200698A (en) * | 2014-04-04 | 2015-11-12 | 日東電工株式会社 | Transparent resin layer, polarizing film with adhesive layer, and image display device |
| TWI681997B (en) * | 2014-06-13 | 2020-01-11 | 日商東亞合成股份有限公司 | Hardened composition |
| KR101724616B1 (en) | 2014-09-18 | 2017-04-07 | 주식회사 엘지화학 | Curable composition used instead of glass |
| KR101828516B1 (en) | 2014-09-18 | 2018-02-12 | 주식회사 엘지화학 | Plastic film and method for preparing the same |
| JP6460901B2 (en) * | 2015-04-28 | 2019-01-30 | 富士フイルム株式会社 | Curable composition, cured film, organic EL display device, liquid crystal display device, touch panel and touch panel display device |
| JP6926863B2 (en) * | 2017-09-11 | 2021-08-25 | 三菱ケミカル株式会社 | Methods for manufacturing polymers for antifouling paints, resin compositions, antifouling paints, coating films, and polymers for antifouling paints |
| CN107866363A (en) * | 2017-09-19 | 2018-04-03 | 广东天安新材料股份有限公司 | A kind of preparation method of home decoration film |
| CN113354968A (en) * | 2020-03-05 | 2021-09-07 | 荒川化学工业株式会社 | Active energy ray-curable resin composition, cured product, laminate, and curing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101652713A (en) * | 2007-04-11 | 2010-02-17 | Lg化学株式会社 | Comprise by the photosensitive resin composition of the prepared polymkeric substance of macromonomer as alkali soluble resins |
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| JPS5859202A (en) * | 1981-10-06 | 1983-04-08 | Kansai Paint Co Ltd | Production of low-molecular, unsaturated vinyl polymer |
| JPH0623326B2 (en) * | 1986-10-20 | 1994-03-30 | 東亞合成化学工業株式会社 | Room temperature dry paint |
| JPH01279982A (en) * | 1988-05-06 | 1989-11-10 | Toagosei Chem Ind Co Ltd | Coating material for plastic |
| JPH0665535A (en) * | 1992-08-19 | 1994-03-08 | Toagosei Chem Ind Co Ltd | Water-based metal-coating resin composition |
| JP2001064318A (en) * | 1999-08-25 | 2001-03-13 | Toagosei Co Ltd | Production of ethylenically unsaturated group- containing graft copolymer |
| JP4486282B2 (en) * | 2001-07-17 | 2010-06-23 | 富士フイルム株式会社 | Pigment dispersant, pigment dispersion composition containing the same, and colored photosensitive composition |
| JP5505855B2 (en) * | 2007-11-28 | 2014-05-28 | 荒川化学工業株式会社 | Active energy ray-curable aqueous material |
| JP5142075B2 (en) * | 2008-01-30 | 2013-02-13 | 荒川化学工業株式会社 | Active energy ray curable resin, active energy ray curable resin composition, and article having a hard coat layer obtained using the same |
| JP2011186140A (en) * | 2010-03-08 | 2011-09-22 | Jsr Corp | Lens for optical module |
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2012
- 2012-09-26 JP JP2012211808A patent/JP6048804B2/en active Active
- 2012-10-30 CN CN201210425440.2A patent/CN103087276B/en not_active Expired - Fee Related
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| CN101652713A (en) * | 2007-04-11 | 2010-02-17 | Lg化学株式会社 | Comprise by the photosensitive resin composition of the prepared polymkeric substance of macromonomer as alkali soluble resins |
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