CN107267054A - Coating film-forming methods - Google Patents

Coating film-forming methods Download PDF

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Publication number
CN107267054A
CN107267054A CN201611167862.9A CN201611167862A CN107267054A CN 107267054 A CN107267054 A CN 107267054A CN 201611167862 A CN201611167862 A CN 201611167862A CN 107267054 A CN107267054 A CN 107267054A
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methyl
coating composition
acrylate
base material
carbamate
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CN201611167862.9A
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CN107267054B (en
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后藤宏太
荻野晋
荻野晋一
松阪裕子
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

There is provided that a kind of adaptation that application face even if base material is complicated shape and base material is also excellent and coating film-forming methods with high intensity.A kind of coating film-forming methods, have：Prepare the process of coating composition (1); the coating composition (1) is containing weight average molecular weight for 550 less than 10; carbamate (methyl) acrylate (A) of 000 scope and 1 intramolecular with more than 2 (methyl) acryloyl groups, weight average molecular weight is 200 less than 550 scope and 1 intramolecular polymerizable unsaturated compound (B) and polymerization initiator (C) with more than 2 polymerism unsaturated groups；The coating composition prepared in foregoing sequence (1) is coated on to the process on base material；The process for solidifying the coating composition (1) on the base material being coated with foregoing sequence, in the implementation of the painting process, the interface of the base material contacted with coating composition (1) reaches the temperature in the range of 28~70 DEG C.

Description

Coating film-forming methods
Technical field
The present invention relates to a kind of coating film-forming methods.
Background technology
At present, for the purpose of to the excellent outward appearance of substrate surface imparting and performance etc., the application on the substrate surface is carried out Coating composition simultaneously makes formed wet coating be solidified to form film.In addition, being used as the coating composition, it is proposed that solvent-borne type Coating composition or carried out by active energy beam the wet coating solidification active energy ray-curable coating material composition (referring for example to patent document 1).From the viewpoint of energy-conservation, productivity ratio raising etc., numerous researchs have been carried out to the latter.
And then, in recent years, in various technical fields, together with the high intensity on the application face of base material, it is desirable to film and The high adhesion of base material.But, it is however generally that, when coating strength is improved, there is the tendency of the adaptation reduction of film and base material. The tendency becomes notable in the case where using active energy ray-curable coating material composition.
In addition, aforementioned coating composition to be applied to outer plate portion, automobile interior exterior member, the household appliances of car body The chance that the application face of product, furniture, construction material etc. constitutes the base material of complicated shape increases.But, in the painting of base material Dress face is complicated shape, such as when combining the shape of multiple planes and/or curved surface, is easily produced by the coating composition structure Into film and base material the insufficient part of adaptation, be peeling or expand sometimes etc. it is bad, as problem.
But, the method on forming the film that excellent adaptation is shown with high intensity and relative to base material, in bag Not yet learning in the prior art containing the technology disclosed in patent document 1.
Prior art literature
Patent document
Patent document 1：International Publication No. 2009/050957
The content of the invention
Invent problem to be solved
Therefore, it is an object of the present invention to provide with high intensity and even in base material application face for complicated shape In the case of forming method with the adaptation of base material also excellent film.
Technical scheme for solving problem
Further investigation is repeated in the present inventor etc. to achieve these goals, as a result finds：Using containing specific Carbamate (methyl) acrylate, specific polymerizable unsaturated compound and polymerization initiator coating composition simultaneously When the coating composition is coated on into base material, by making the coating composition and the temperature at the interface of the base material reach specific temperature Spend scope, it is possible to achieve above-mentioned purpose.
I.e. the present invention is as described below.
1. a kind of coating film-forming methods, it is characterised in that have：
Process (1)：Prepare the process of coating composition (1), the coating composition (1) is 550 containing weight average molecular weight Less than in the range of 10,000 and 1 intramolecular has the carbamate (first of more than 2 (methyl) acryloyl group Base) acrylate (A), weight average molecular weight be 200 less than in the range of 550 and 1 intramolecular has the polymerization of more than 2 The polymerizable unsaturated compound (B) and polymerization initiator (C) of property unsaturated group；
Process (2)：The coating composition (1) prepared in the process (1) is coated on to the process on base material；
Process (3)：The process for solidifying the coating composition (1) on the base material being coated with the process (2), wherein
In the implementation of the process (2), the interface of the base material contacted with the coating composition (1) reaches 28~ Temperature in the range of 70 DEG C.
2. the coating film-forming methods according to above-mentioned 1, wherein, the coating composition (1) is containing weight average molecular weight 550 less than in the range of 10,000 and 1 intramolecular has (methyl) acryloyl group of more than 2 and more than 1 is gathered Carbamate (methyl) acrylate (A11) of alkylidene oxide chain is used as the carbamate (methyl) acrylate (A) at least its a kind.
3. the coating film-forming methods according to above-mentioned 1 or 2, wherein, the coating composition (1) contains weight average molecular weight For 550 less than in the range of 10,000 and 1 intramolecular have more than 2 (methyl) acryloyl group and more than 1 Carbamate (methyl) acrylate (A12) of cyclohexane ring is used as the carbamate (methyl) acrylate (A) At least its a kind.
4. the coating film-forming methods according to any one of above-mentioned 1 to 3, wherein, the coating composition (1) contains weight Average molecular weight is 550 less than in the range of 10,000 and 1 intramolecular has (methyl) acryloyl group and 1 of more than 2 Carbamate (methyl) acrylate (A13) of chlorinated isocyanurates ring more than individual is used as the carbamate (methyl) third At least its a kind of olefin(e) acid ester (A).
5. the coating film-forming methods according to any one of above-mentioned 1 to 4, wherein, the coating composition (1) contains tool Have the polymerizable unsaturated compound (B ') of polyoxyalkylene chain as the polymerizable unsaturated compound (B) at least its 1 kind.
6. the coating film-forming methods according to any one of above-mentioned 1 to 5, wherein, for the coating composition (1), When being set to amount to 100 mass parts by the nonvolatile component of the coating composition (1), carbamate (methyl) acrylic acid Ester (A) is 10 to 80 mass parts, and the polymerizable unsaturated compound (B) is 20 to 90 mass parts.
7. the coating film-forming methods according to any one of above-mentioned 1 to 6, wherein, in the coating composition (1), no Volatile ingredient accounts for 90 to 100 quality %.
8. the coating film-forming methods according to any one of above-mentioned 1 to 7, wherein, the process (2) is in advance will be with The interface of the base material of coating composition (1) contact is heated to after the temperature in the range of 28 to 70 DEG C, will be described Coating composition (1) is coated on the process on the base material.
9. the coating film-forming methods according to any one of above-mentioned 1 to 8, wherein, the process (2) is to be advance by described in Coating composition (1) is heated to after the temperature in the range of 28 to 70 DEG C, and the coating composition (1) is coated on into the base material On process.
10. the coating film-forming methods according to any one of above-mentioned 1 to 9, wherein, in the process (3), described poly- Initiator (C) is closed in the case of Photoepolymerizationinitiater initiater (C1), active energy beam is irradiated to the coating composition (1), In the case that the polymerization initiator (C) is thermal polymerization (C2), the coating composition (1) is heated.
Invention effect
The coating film-forming methods of the present invention are characterised by possessing the process (1)~(3), especially in the process (2) Implementation in, the interface of the base material contacted with coating composition (1) reaches the temperature in the range of 28~70 DEG C, therefore, it can Formed with high intensity and in the case of being complicated shape even in the application face of base material with the adaptation of base material also excellent painting Film.
Embodiment
Hereinafter, the coating film-forming methods of the present invention are illustrated in further detail.
First, process (1) is illustrated.
Process (1) in the coating film-forming methods of the present invention is the process of preparation coating composition (1), the Coating material composition Thing (1) is 550 less than in the range of 10,000 and 1 intramolecular has (methyl) of more than 2 containing weight average molecular weight Carbamate (methyl) acrylate (A) of acryloyl group, weight average molecular weight be 200 less than in the range of 550 and 1 intramolecular has the polymerizable unsaturated compound (B) and polymerization initiator (C) of the polymerism unsaturated group of more than 2.
[carbamate (methyl) acrylate (A)]
Carbamate (methyl) acrylate (A) is the acryloyl group and methacryl that 1 intramolecular has more than 2 At least one and weight average molecular weight of base are 550 less than the carbamate compounds in the range of 10,000.
Wherein, from the viewpoint of the film and the adaptation of base material and coating strength formed, above-mentioned carbamate (methyl) acrylate (A) preferably has average 2~4 (methyl) acryloyl groups, further preferred 1 intramoleculars in 1 intramolecular There are average 2~3 acryloyl groups with average 2~3 (methyl) acryloyl groups, particularly preferred 1 intramolecular.This explanation In book, the average of (methyl) acryloyl group of the intramolecular of compound 1 is by the compound used raw material when synthesizing The theoretical value that is calculated of equivalent proportion.
It is explained, in this specification, " (methyl) acrylate " refers to acrylate or methacrylate." (first Base) acrylic acid " refer to acrylic or methacrylic acid.In addition, " (methyl) acryloyl group " refers to acryloyl group or metering system Acyl group.In addition, " (methyl) acrylamide " refers to acrylamide or Methacrylamide.
In addition, the weight average molecular weight of above-mentioned carbamate (methyl) acrylate (A) is more than 550 as described above and low In the range of 10,000.When weight average molecular weight is less than 550, the adaptation of film and base material is deteriorated, on the contrary, its be 10,000 with When upper, appearance of film and coating strength are deteriorated.From appearance of film, the adaptation of the film formed and base material and coating strength Viewpoint is set out, in the range of preferably 750~5,000, further preferred 1,000~3,500.
It is explained, in this specification, weight average molecular weight is the retention time that gel permeation chromatography (GPC) will be used to determine (holding capacity) (keeps holding by the retention time of polystyrene standard known to the molecular weight that is measured under the same conditions Amount) value that is scaled the molecular weight of polystyrene and obtains.Specifically, as gel permeation chromatography device, " HLC- is used 8120GPC " (trade name, East ソ ー societies system), as post, use " TSKgel G4000HXL ", " TSKgel G3000HXL ", " TSKgel G2500HXL " and " TSKgel G2000HXL " (trade name, Jun Wei East ソ ー societies system) amount to 4, be used as detection The condition that it is 40 DEG C that device, which can be tetrahydrofuran in mobile phase using differential refraction rate meter, determine temperature, flow velocity is 1mL/min Under be measured.
In addition, from the viewpoint of the film and the adaptation of base material and coating strength formed, above-mentioned carbamate The glass transition temperature (Tg) of (methyl) acrylate (A) be 10 DEG C~80 DEG C, be preferably 30 DEG C~50 DEG C in the range of i.e. Can.
It is explained, in this specification, the glass transition temperature of above-mentioned carbamate (methyl) acrylate (A) (Tg) it is static glass transition temperature.The static glass transition temperature (such as) can be measured in the following manner： Materials in determining in cup, carry out vacuum attraction and after removing solvent completely, use differential scanning calorimeter " DSC-50Q types " (Shimadzu Seisakusho Ltd.'s system, trade name) determines thermal change with 3 DEG C/min of programming rate in the range of -100 DEG C~150 DEG C, The change point of the initial baseline of low temperature side is set to static glass transition temperature.
As above-mentioned carbamate (methyl) acrylate (A), for example, it can use：By making polyisocyanates chemical combination Thing (a1), 1 intramolecular have (methyl) propylene of the hydroxyl of more than 1 and the hydroxyl of more than 1 (methyl) acryloyl group The chain lengthening composition (a4) of acid esters (a2) and polyol compound (a3) as needed and/or hydroxy-containing compounds reacts and obtained Carbamate (methyl) acrylate (A1) arrived；By make above-mentioned polyol compound (a3), 1 intramolecular have 1 with On NCO and more than 1 (methyl) acryloyl group (methyl) acrylate (a5) and root containing NCO Obtained from chain lengthening composition (a4) reaction according to the above-mentioned polyisocyanate compound (a1) and/or hydroxy-containing compounds of needs Carbamate (methyl) acrylate (A2) etc..
[polyisocyanate compound (a1)]
Above-mentioned polyisocyanate compound (a1) is the compound for the NCO that 1 intramolecular has more than 2.As The polyisocyanate compound (a1), can be enumerated for example：Hexamethylene diisocyanate, the isocyanic acid of tri-methyl hexamethylene two The aliphatic diisocyanate such as ester, dimer acid diisocyanate, lysine diisocyanate compound and these diisocyanate Urea diketone type addition product, adduct type addition product, biuret form addition product, chlorinated isocyanurates cycloaddition thing；Isophorone two Isocyanates, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), hexahydrotoluene -2,4- diisocyanate, hexahydrotoluene - 2,6- diisocyanate, 1,3- bis- (isocyanatomethyl) hexamethylene, 1,4- bis- (isocyanatomethyl) hexamethylene, 1,4- The alicyclic diisocyanates such as cyclohexane diisocyanate, 1,3- pentamethylene diisocyanate, 1,2- cyclohexane diisocyanates Urea diketone type addition product, adduct type addition product, biuret form addition product, the isocyanuric acid of compound and these diisocyanate Ester cycloaddition thing；Xylylene diisocyanate, an xylylene diisocyanate, tetramethyl xylylene diisocyanate, Toluene di-isocyanate(TDI), 4,4 '-methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanates, 1,4- naphthalene diisocyanates, 4, 4 '-toluidine diisocyanate, 4,4 '-diphenyl ether diisocyanate, metaphenylene diisocyanate, to the isocyanide of phenylene two Acid esters, 4,4 '-biphenylene diisocyanate, 3,3 '-dimethyl -4,4 '-biphenylene diisocyanate, double (4- isocyanic acids Root closes phenyl) aromatic diisocyanate compounds and these two isocyanic acids such as sulfone, isopropylidene double (4- phenyl isocyanates) Urea diketone type addition product, adduct type addition product, biuret form addition product, the chlorinated isocyanurates cycloaddition thing of ester；Triphenyl first Alkane -4,4 ', 4 "-triisocyanate, the isocyanato- benzene of 1,3,5- tri-, the isocyanato- toluene of 2,4,6- tri-, 4,4 '-dimethyl Diphenyl methane -2,2 ', the polyisocyanic acid in the molecule of 5,5 '-tetraisocyanate etc. 1 with the NCO of more than 3 is esterified Urea diketone type addition product, adduct type addition product, biuret form addition product, the chlorinated isocyanurates of compound and these polyisocyanates Cycloaddition thing；Relative to ethylene glycol, propane diols, 1,4- butanediols, dihydromethyl propionic acid, PAG, trihydroxy methyl third The hydroxyl of the polyalcohol of alkane, hexanetriol etc. turns into excessive ratio with NCO forms polyisocyanate compound reaction Urethane addition product and these polyisocyanates biuret form addition product, chlorinated isocyanurates cycloaddition thing etc..
[(methyl) acrylate (a2) of hydroxyl]
(methyl) acrylate (a2) of the hydroxyl is 1 intramolecular with the hydroxyl of more than 1 and more than 1 The compound of (methyl) acryloyl group.
As (methyl) acrylate (a2) of the hydroxyl, it can enumerate for example：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) such as (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls The monoesters compound of 2 yuan of alcohol of acrylic acid and carbon number 2~8；It is somebody's turn to do the list of 2 yuan of alcohol of (methyl) acrylic acid and carbon number 2~8 The 6-caprolactone modified body of carboxylate；N- hydroxymethyls (methyl) acrylamide；Allyl alcohol so with molecular end be hydroxyl Polyoxyalkylene chain (methyl) acrylate；Glycerine two (methyl) acrylate, trimethylolpropane two (methyl) third Two (methyl) acrylate compounds such as olefin(e) acid ester, pentaerythrite two (methyl) acrylate；Pentaerythrite three (methyl) propylene Acid esters etc. three (methyl) acrylate compounds etc..
[polyol compound (a3)]
The polyol compound (a3) is beyond (methyl) acrylate (a2) of above-mentioned hydroxyl, 1 intramolecular tool There is the compound of the hydroxyl of more than 2.
As the polyol compound (a3), it can enumerate for example：Ethylene glycol, propane diols, diethylene glycol, trimethylene two Alcohol, tetraethylene glycol, triethylene glycol, DPG, 1,4- butanediols, 1,3 butylene glycol, 2,3- butanediols, 1,2- butanediols, 2- Methyl-1,3-propanediol, 3- methyl isophthalic acids, 2- butanediols, 2-butyl-2-ethyl-1,3-propanediol, 1,2- pentanediols, 1,5- penta Glycol, 1,4- pentanediols, 2,4-PD, 2,3- dimethyltrimethylenes glycol, tetramethylene glycol, 3- methyl -4,3- penta Glycol, 3- methyl isophthalic acids, 5- pentanediols, 2,2,4- trimethyl -1,3- pentanediols, 1,6-HD, 1,5- hexylene glycols, 1,4- oneself two Alcohol, 2,5-HD, neopentyl glycol, 1,4 cyclohexane dimethanol, Tricyclodecane Dimethanol, 3-hydroxypivalic acid DOPCP, 2 yuan of alcohol such as hydrogenated bisphenol A, A Hydrogenated Bisphenol A F, dihydromethyl propionic acid；Addition has the lactone compounds such as 6-caprolactone in these 2 yuan of alcohol The polylactone diol of thing；The esterdiol compounds such as double (ethoxy) terephthalates；It is the alkylene oxide adducts of bisphenol-A, poly- Ethylene glycol, polypropylene glycol, polytetramethylene glycol etc. have the polyol compound of polyoxyalkylene chain；Glycerine, trimethylolethane, Trimethylolpropane, two glycerine, triglycerin, 1,2,6- hexanetriols, pentaerythrite, dipentaerythritol, three (2- ethoxys) isocyanides The alcohol that more than 3 yuan of uric acid, D-sorbite, mannitol etc.；Addition has 6-caprolactone etc. to lactonize in these more than 3 yuan alcohol The poly-lactone polyol compound of compound；Fatty acid ester compound of glycerine etc..
[the chain lengthening compositions (a4) of hydroxy-containing compounds]
The chain lengthening composition (a4) of the hydroxy-containing compounds is (methyl) acrylate that can be with the hydroxyl And the compound of the hydroxyl such as polyol compound (a3) is reacted and makes the compound of molecule chain lengthening (a2).
As the chain lengthening composition (a4) of the hydroxy-containing compounds, it can enumerate for example：In 6-caprolactone, gamma-valerolactone etc. Ester compounds；Epoxyalkane compound such as oxirane, expoxy propane etc..
[(methyl) acrylate (a5) containing NCO]
Described (methyl) acrylate (a5) containing NCO is the NCO that 1 intramolecular has more than 1 And the compound of more than 1 (methyl) acryloyl group.
As (methyl) acrylate (a5) containing NCO, it can enumerate for example：Isocyanatomethyl (methyl) Acrylate, isocyanate ethyl (methyl) acrylate, isocyanates propyl group (methyl) acrylate, isocyanates butyl (methyl) acrylate, isocyanates octyl group (methyl) acrylate, to methacryloxy-α, α '-dimethyl benzyl is different Cyanate, acryloxy-α, α '-dimethyl benzyl isocyanate, or to isopropenyl-α, α '-dimethyl benzyl is different Double ((methyl) acryloyloxymethyl) ethyl isocyanates of cyanate, 1,1-, 1 mole of hydroxyalkyl (methyl) acrylate and two The reaction product that 1 mole of isocyanate compound, specifically enumerates for example (anti-by having for IPDI etc Answering property is different) compound and (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 4- hydroxyl fourths of 2 NCOs Compound etc. obtained from the equimolar addition reaction of the polymerism unsaturated monomer of the hydroxyls such as ester.
Above-mentioned carbamate (methyl) acrylate (A) can be by making the composition of hydroxyl and containing NCO Composition carries out known urethane reaction and synthesized.Above-mentioned reaction can generally be carried out in organic solution.As having Machine solvent, can be enumerated：The aromatic hydrocarbon series solvents such as toluene, dimethylbenzene, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone Etc. ester series solvents such as ketone series solvent, ethyl acetate, propyl acetate, i-butyl base, butyl acetate etc..These can be used as a kind Or mixture of more than two kinds is used.Reaction temperature is preferably normal temperature~100 DEG C, and the reaction time is preferably 1~10 hour.
In the reaction of above-mentioned urethane, reaction can be confirmed by the isocyanate equivalent of following response liquid Carry out state.The isocyanate equivalent can be obtained by using the back titration for having dibutylamine.The back titration is specifically It can carry out in the following manner：Excessive dibutylamine is added in the sample and it is reacted, and titration is used as using bromophenol blue Indicator and the dibutylamine that remnants are titrated with aqueous hydrochloric acid solution.
In above-mentioned reaction, dibutyl tin laurate, dibutyl tin diethyl hexaoate, sulfurous can be used as needed The organotin catalysts such as sour dibutyl tin.The amount of catalyst relative to the mass parts of total amount 100 of reaction raw materials be preferably 0.01~ 1.0 mass parts, more preferably 0.1~0.5 mass parts.Further, it is possible to use the polymerization inhibitor such as hydroquinone monomethyl ether.Use polymerization In the case of inhibitor, its addition is preferably 0.01~1.0 mass parts relative to the mass parts of total amount 100 of reaction raw materials.
As above-mentioned carbamate (methyl) acrylate (A), from the film formed and the sight of the adaptation of base material Point sets out, carbamate (methyl) acrylate (A11) preferably with polyoxyalkylene chain, wherein, from further carrying The adaptation of the film that is formed of height and base material and from the viewpoint of applying film strength, more preferably with polyoxyalkylene chain and Carbamate (methyl) acrylate (A11 ') of cyclohexane ring.
Wherein, it is above-mentioned that there is polyoxygenated from the viewpoint of the film and the adaptation of base material and coating strength formed Carbamate (methyl) acrylate (A11) of alkylidene chain preferably has average 1~100 polyoxygenated Asia in 1 intramolecular Alkyl chain, further preferably there are average 2~80 polyoxyalkylene chains in 1 intramolecular, particularly preferably have in 1 intramolecular Average 10~60 polyoxyalkylene chains.In this specification, the polyoxyalkylene chain of the intramolecular of compound 1 is averaged Number is by the theoretical value that the equivalent proportion of used raw material is calculated when synthesizing in the compound.
Above-mentioned carbamate (methyl) acrylate (A11) with polyoxyalkylene chain for example can be by following Method is manufactured：As at least its a kind of (methyl) acrylate (a2) of the hydroxyl, using sub- with the polyoxygenated The method of (methyl) acrylate of the hydroxyl of alkyl chain；As at least its a kind of the polyol compound (a3), use Method of polyol compound with the polyoxyalkylene chain etc..
In addition, as above-mentioned carbamate (methyl) acrylate (A), going out from the viewpoint of the painting film strength formed Hair, it is also preferred that carbamate (methyl) acrylate (A12) with cyclohexane ring.Carbamate with cyclohexane ring (methyl) acrylate (A12) can for example be manufactured by the following method：It is used as the polyisocyanate compound (a1) At least its a kind, use method of the polyisocyanate compound with the cyclohexane ring etc..
Wherein, it is above-mentioned that there is hexamethylene from the viewpoint of the film and the adaptation of base material and coating strength formed Carbamate (methyl) acrylate (A12) of ring is preferably to have average 1~60 cyclohexane ring in 1 intramolecular, enter one Step preferably has average 4~50 cyclohexane rings, particularly preferably in 1 intramolecular with average 8~40 hexamethylenes in 1 intramolecular Ring.In this specification, the average of the cyclohexane ring of the intramolecular of compound 1 is by being used in the compound when synthesizing Raw material the theoretical value that is calculated of equivalent proportion.
In addition, as above-mentioned carbamate (methyl) acrylate (A), going out from the viewpoint of the painting film strength formed Hair, it is also preferred that carbamate (methyl) acrylate (A13) with chlorinated isocyanurates ring, wherein, improve institute from further From the viewpoint of the film of formation and the adaptation of base material and painting film strength, more preferably with polyoxyalkylene chain and isocyanide Carbamate (methyl) acrylate (A13 ') of urate ring.
Wherein, it is above-mentioned that there is isocyanide urine from the viewpoint of the film and the adaptation of base material and coating strength formed Carbamate (methyl) acrylate (A13) of acid esters ring preferably has average 1~10 chlorinated isocyanurates in 1 intramolecular Ring, further preferably 1 intramolecular have average 1~8 chlorinated isocyanurates ring, particularly preferably have average 1 in 1 intramolecular~ 6 chlorinated isocyanurates rings.In this specification, the average of the chlorinated isocyanurates ring of the intramolecular of compound 1 is by changing at this The theoretical value that the equivalent proportion of used raw material is calculated during the synthesis of compound.
Above-mentioned carbamate (methyl) acrylate (A13) with chlorinated isocyanurates ring for example can be by with lower section Method is manufactured：As at least its a kind of the polyisocyanate compound (a1), using with many of the chlorinated isocyanurates ring Method of isocyanate compound etc..
Carbamate (methyl) acrylate (A) can be used alone or combine two or more and use.
[polymerizable unsaturated compound (B)]
Polymerizable unsaturated compound (B) is that weight average molecular weight is 200 less than in the range of 550 and 1 intramolecular Polymerizable unsaturated compound with the polymerism unsaturated group of more than 2.Wherein, from the film and base material formed From the viewpoint of adaptation, coating strength, polymerizable unsaturated compound (B) 1 intramolecular have average 2~4, preferably 2 ~3 polymerism unsaturated groups.
In addition, the weight average molecular weight of above-mentioned polymerizable unsaturated compound (B) is as described above for 200 less than 550. When weight average molecular weight is less than 200, the film and the adaptation of base material formed is deteriorated, on the contrary, when it is more than 550, outside film The film and the adaptation and coating strength of base material see, formed is deteriorated.From the close of appearance of film, the film formed and base material From the viewpoint of conjunction property, coating strength, the weight average molecular weight of above-mentioned polymerizable unsaturated compound (B) is preferably 200~400, More preferably 200~300.
In addition, from the viewpoint of appearance of film, the adaptation of the film formed and base material, coating strength, it is above-mentioned poly- The unsaturated group equivalent of conjunction property unsaturated compound (B) is preferably 100~250g/mol, more preferably 100~200g/ Mol, further particularly preferably 100~150g/mol.
In this specification, unsaturated group equivalent is the quality of the compound per polymerism unsaturated group 1mol, for Value (g/mol) obtained by the quality of compound divided by the polymerism unsaturated group amount being present in compound.In this specification, Above-mentioned unsaturated group equivalent is the theoretical value that is calculated by the quality of the raw material used when synthesizing in compound.
As above-mentioned polymerizable unsaturated compound (B), the carboxylate of such as polyalcohol and (methyl) acrylic acid can be enumerated Deng.Specifically, it can enumerate for example：Ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, three second two Alcohol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, DPG two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, four propane diols two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, 1,4- butanediols Two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6- oneself two Alcohol two (methyl) acrylate, bisphenol-A epoxy oxide-modified two (methyl) acrylate, isocyanuric acid ethylene-oxide-modified two Two (the first such as (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, isobide two (methyl) acrylate Base) acrylate compounds；Glycerine three (methyl) acrylate, glycerol epoxy oxide-modified three (methyl) acrylate, glycerine Epoxy pronane modification three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane epoxy second Alkane is modified three (methyl) acrylate, trimethylolpropane epoxy pronane modification three (methyl) acrylate, isocyanuric acid epoxy Oxide-modified three (methyl) acrylate, pentaerythrite three (methyl) acrylate, 6-caprolactone are modified three (acryloxy second Base) three (methyl) acrylate compounds such as chlorinated isocyanurates；Pentaerythrite four (methyl) acrylate, pentaerythrite epoxy second Alkane is modified four (methyl) acrylate, pentaerythrite epoxy pronane modification four (methyl) acrylate, two trimethylolpropanes four (methyl) acrylate, two trimethylolpropanes ethylene-oxide-modified four (methyl) acrylate, two trimethylolpropane epoxies Propane is modified four (methyl) acrylate, two glycerine four (methyl) acrylate, (methyl) third of two glycerol epoxies oxide-modified four Olefin(e) acid ester, two glycerol epoxy propane are modified four (methyl) acrylate compounds such as four (methyl) acrylate；In addition two season penta Tetrol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc..
Above-mentioned polymerizable unsaturated compound (B) can be used alone or combine two or more and use.
In the present invention, from the viewpoint of the film and the adaptation of base material formed, it is used as the polymerism insatiable hunger With compound (B), the polymerizable unsaturated compound (B ') preferably with polyoxyalkylene chain.
[polymerization initiator (C)]
Polymerization initiator (C) is the polymerization initiator in Photoepolymerizationinitiater initiater (C1) and thermal polymerization (C2). Wherein, due to coating excellent storage stability so that suppress base material thermal deformation, while the adaptation with base material can be formed Film excellent and with high intensity, it is therefore preferable that using Photoepolymerizationinitiater initiater (C1) as the polymerization initiator (C) extremely It is few a kind.
In addition, as above-mentioned polymerization initiator (C), above-mentioned Photoepolymerizationinitiater initiater (C1) being applied in combination and thermal polymerization is drawn Send out agent (C2).It is explained, in following processes (3), in the case of carrying out active energy beam irradiation, is triggered using photopolymerization Agent (C1) is at least one kind of as above-mentioned polymerization initiator (C), in the case where being heated, and uses thermal polymerization (C2) It is used as at least one kind of of the polymerization initiator (C).
It is the base material that thermal deformation easily occurs for organic material etc. in the base material in the envelope forming method of the present invention When, active energy beam is carried out using Photoepolymerizationinitiater initiater (C1) as above-mentioned polymerization initiator (C) and in following processes (3) Irradiation can suppress the thermal deformation of base material, while formed with the excellent adhesion of base material and the film with high intensity, therefore excellent Choosing.
[Photoepolymerizationinitiater initiater (C1)]
Photoepolymerizationinitiater initiater (C1) produces the change of free radical (being also the form of intermediate) for absorption active energy beam Compound, can be the mixture of compound of more than two kinds.As Photoepolymerizationinitiater initiater (C1), it can enumerate：Can photochemically it activate Compound (such as benzoin), the combination and their mixing of chromophore and coinitiator (such as benzophenone and tertiary amine) Thing, (such as thioxanthones and tertiary amine) of sensitizer and coinitiator or the group with (such as the thioxanthones and amino ketones) of chromophore Conjunction, H2O2With the electron transport equity of redox system, dyestuff and the borate and/or amine etc. such as the combination of iron (II) salt.
As Photoepolymerizationinitiater initiater (C1), specifically, it can enumerate for example：The α of benzyl, diacetyl etc.-diketonate Compound；The acyloin coms such as benzoin；The acyloins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether etherificate is closed Thing；The thioxanthone compounds such as thioxanthones, 2,4- diethyl thioxanthones, ITX, thioxanthones -4- sulfonic acid；Hexichol first Ketone, o-methyl-benzene formylbenzoate ester, 4- methyl benzophenones, 4- phenyl benzophenones, 4,4 '-bis- (dimethylaminos) two The benzophenone cpds such as Benzophenone, 4,4 '-bis- (diethylamino) benzophenone；Michler's keton compound；Acetophenone, 2- (4- Tosyloxy) -2- phenyl acetophenones, to dimethylamino benzoylformaldoxime, α, α '-dimethoxy acetoxyl group benzophenone, 2,2 '-dimethoxy -2- phenyl acetophenones, acetanisole, 2- methyl [4- (methyl thio) phenyl] -2- morpholinoes - 1- acetone, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls)-butane -1- ketone, α-different hydroxyisobutyl benzophenone, α, The acetophenone compounds such as the chloro- 4- metaphenoxy acetophenones of α '-two, 1- hydroxy-cyclohexyl-phenyl -one；2,4,6- trimethylbenzoyls The acylphosphine oxide compounds such as base diphenyl phosphine oxide, double (acyl group) phosphine oxides；The quinones such as anthraquinone, 1,4- naphthoquinones；Phenacyl The halogen compounds such as chlorine, trihalomethyl phenylsulfone, three (trihalomethyl)-s- triazines；The peroxide such as di-t-butyl peroxide Deng.
As Photoepolymerizationinitiater initiater (C1) commercially available product, it can enumerate for example：イルガキュア(IRGACURE)-127、 イルガキュア-184、イルガキュア-261、イルガキュア-369、イルガキュア-500、イルガキ ュア-651、イルガキュア-754、イルガキュア-819、イルガキュア-907、イルガキュア-CGI- 1700th, イ Le ガ キ ュ ア -2959, イ Le ガ キ ュ ア-TPO, ダ ロ キ ュ ア (Darocur) -1173 (are BASF above Society's system, trade name)；カ ヤ キ ュ ア ー-DETX-S, カ ヤ キ ュ ア ー-EPA (are Japanese chemical drug society system, commodity above Name)；ESACURE KIP 150, ESACURE ONE (LAMBERTI societies system, trade name)；SB-PI701、SB-PI703、SB- PI704、SB-PI705、SB-PI707、SB-PI710、SB-PI711、SB-PI712、SB-PI714、SB-PI716、SB- PI718、SB-PI719、SB-PI751、SB-PI759、SB-PI769、SB-PI777、SB-PI799、SB-PI818、SB- PI850, SB-PI865, SB-PI8100 (being society of Shuan Bang industry joint stock company limited system, trade name above) etc..
Above-mentioned Photoepolymerizationinitiater initiater (C1) can individually using or two or more combination and use.Alternatively, it is also possible to simultaneously With it is described have more than 2 photopolymerization initiation portion Photoepolymerizationinitiater initiater (C1-1) and the Photoepolymerizationinitiater initiater beyond it.
[thermal polymerization (C2)]
Thermal polymerization (C2) for produced by heating free radical (being also the form of intermediate) compound or this The mixture of a little compounds.As thermal polymerization (C2), it can enumerate for example：Benzoyl peroxide, caprylyl peroxide, mistake Aoxidize lauroyl, stearoyl, cumene hydroperoxide, tert-butyl peroxide, tert-butyl hydroperoxide laurate, tertiary fourth The organic peroxides such as base isopropyl peroxide carbonic ester, tert-butyl hydroperoxide acetate, di-isopropylbenzene hydroperoxide；Azo is double Isobutyronitrile, azo double (2,4- methyl pentane nitriles), azo double (2- methyl propionitrile), azo double (2- methylbutyronitriles), 4,4 '-azos Double (4- cyano butyric acids), dimethyl azo double (2 Methylpropionic acid esters), double [2- methyl-N- (2- the hydroxyethyls)-propionyl of azo Amine], the azo-compound such as azo double { 2- methyl-N- [2- (1- hydroxybutyls)]-propionamide }；Potassium peroxydisulfate, ammonium persulfate, mistake Persulfates such as sodium sulphate etc..
As thermal polymerization (C2) commercially available product, it can enumerate for example：VA-044、VA-046B、V-50、VA-057、 VA-061, VA-067, VA-086, V-60, V-70, V-65, V-601, V-59, V-40, VF-096, VAm-110 (be above and Wako Pure Chemical Industries society system, trade name), パ ー Block チ Le H, パ ー オ Network タ O (being You societies system, trade name above) etc..
Above-mentioned thermal polymerization (C2) can reduce as needed and with sugar, rongalite, iron complex etc. Agent and as redox initiator.Above-mentioned thermal polymerization (C2) can be used alone or combine two or more and use.
[coating composition (1)]
Coating composition (1) used in the present invention is to contain above-described carbamate (methyl) acrylate (A), the coating composition of polymerizable unsaturated compound (B) and polymerization initiator (C).
From the viewpoint of the film and the adaptation of base material, coating strength formed, by the coating composition (1) When nonvolatile component is set to amount to 100 mass parts, carbamate (methyl) acrylate (A) in coating composition (1) and The mixing ratio of polymerizable unsaturated compound (B) is preferably in following scopes.
Carbamate (methyl) acrylate (A)：10~80 mass parts, preferably 15~70 mass parts, further preferably 20~60 mass parts.
Polymerizable unsaturated compound (B)：20~90 mass parts, preferably 25~80 mass parts, further preferred 30~70 Mass parts.
In addition, from the viewpoint of the film and the adaptation of base material, coating strength formed, relative to mentioned component (A) polymerization initiator (C) in, (B) and (C) nonvolatile component 100 mass parts of total, coating composition (1) is no Volatile ingredient use level is 0.1~20 mass parts, preferably 0.5~15 mass parts, the model of more preferably 1.0~10 mass parts In enclosing.
It is explained, in this specification, nonvolatile component refers to constitute in the composition of coating composition in addition to the solvents Whole compositions.
Coating composition (1) can also contain ultra-violet absorber and/or light stabilizer.It is used as above-mentioned ultraviolet radiation absorption Agent, can use currently known ultra-violet absorber, can for example use enumerate BTA system absorbent, triazine system absorbent, Salicyclic acid derivatives system absorbent, benzophenone series absorbent etc..In addition, above-mentioned ultra-violet absorber can have polymerism not Saturated group.
As the concrete example of enumerate BTA system absorbent, it can enumerate：2- (2 '-hydroxyl -5 '-aminomethyl phenyl) BTA, 2- (2 '-hydroxyl -5 '-tert-butyl-phenyl) BTA, 2- (2 '-hydroxyl -3 ', 5 '-di-t-butyl phenyl) BTA, 2- (2 '-hydroxyl -3 '-the tert-butyl group -5 '-aminomethyl phenyl) -5- chlorobenzotriazoles, 2- (2 '-hydroxyl -3 ', 5 '-di-t-butyl phenyl) - 5- chlorobenzotriazoles, 2- (2 '-hydroxyl -3 ', 5 '-two-tertiary pentyl phenyl) BTA, 2- (2 '-hydroxyl -4 '-octyloxy benzene Base) BTA, 2- { 2 '-hydroxyl -3 '-(3 ", 4 ", 5 ", 6 "-tetrahydric phthalimide methyl) -5 '-aminomethyl phenyl } benzene And triazole, 2- [2- hydroxyls -5- [2- (methacryloxy) ethyl] phenyl] -2H- BTAs etc..
As the concrete example of triazine system absorbent, it can enumerate：(2- hydroxyls -4- is different by double (2,4- the 3,5-dimethylphenyls) -6- of 2,4- Octyloxyphenyl) -1,3,5- triazines, 2- [4 ((2- hydroxyl -3- dodecyloxies propyl group)-epoxide) -2- hydroxy phenyls] -4,6- Double (2,4- 3,5-dimethylphenyls) -1,3,5- triazines, 2- [4- ((2- hydroxyl -3- tridecane epoxides propyl group)-epoxide) -2- hydroxy benzenes Base] -4,6- pairs of (2,4- 3,5-dimethylphenyls) -1,3,5- triazines, double (the 2,4- dimethyl benzenes of 2- (2,4- dihydroxy phenyls) -4,6- Base) -1,3,5- triazines etc..
As the concrete example of salicyclic acid derivatives system absorbent, it can enumerate：Phenyl salicylic acid esters, to octyl phenyl salicylic acid Ester, 4- tert-butylphenyl salicylate acid esters etc..
As the concrete example of benzophenone series absorbent, it can enumerate：4- dihydroxy benaophenonels, 2- hydroxyl -4- methoxyl groups Benzophenone, 2,2 '-dihydroxy -4- methoxy benzophenones, -2 '-carboxyl benzophenone of 2- hydroxyl -4- methoxyl groups, 2- hydroxyls - 4- methoxyl group -5- diphenylsulfone ketones trihydrate, 2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenone, 2- hydroxyls -4- be pungent Epoxide benzophenone, 2- hydroxyl -4- octadecane epoxides benzophenone, sodium 2,2 '-dihydroxy -4,4 '-dimethoxy -5- sulfo groups two Benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 4- dodecyloxy -2- dihydroxy benaophenonels, 5- chlorine-2-hydroxyl hexichol first Ketone, resorcinol monobenzoate, 2,4- dibenzoyl resorcinols, 4,6- dibenzoyl resorcinols, hydroxyl 12 Alkylbenzophenones, 2,2 '-dihydroxy -4 (3- methacryloxy -2- hydroxy propyloxy groups) benzophenone etc..
In addition, as the commercially available product of above-mentioned ultra-violet absorber, can enumerate for example：TINUVIN900、TINUVIN 928、 TINUVIN 348-2, TINUVIN 479, TINUVIN 405, TINUVIN 400, (BASF societies system, trade name, TINUVIN チ ヌ PVC Application is registration mark), the chemical society's system of the (great mound of RUVA 93, trade name) etc..
In the case that coating composition (1) contains above-mentioned ultra-violet absorber, the use level of the ultra-violet absorber is relative In the range of the nonvolatile component total amount of coating composition (1), preferably 0.5~10 mass %, more preferably 0.8~9 matter Measure %, more preferably 1.0~8 mass %.
The light stabilizer is used as the free radical chain of the living radical species generated in the deterioration process of seizure film Inhibitor, can be enumerated such as the light stabilizer of hindered amine compound.
As the light stabilizer that excellent Photostabilised effect is shown in light stabilizer, hindered piperidine chemical combination can be enumerated Thing.As hindered piperidine compound, it can enumerate for example：Double (1,2,2,6,6- pentamethyl -4- piperidyls) sebacates, it is double (2, 2,6,6- tetramethyl -4- piperidyls) sebacate, double (N- methyl -2,2,6,6- tetramethyl -4- piperidyls) sebacates, 4- Benzoyloxy -2,2 ', 6,6 '-tetramethyl piperidine, double (1,2,2,6,6- pentamethyl -4- piperidyls) { [double (1,1- bis- of 3,5- Methylethyl) -4- hydroxy phenyls] methyl the haplotype such as butylpropionate material；Poly- { [6- (1,1,3,3- tetramethyl butyls) Imino group -1,3,5- triazine -2,4- diyls] [(2,2,6,6- tetramethyl -4- piperidyls) imino group] hexa-methylene [(2,2,6, 6- tetramethyl -4- piperidyls) imido alcohol] etc. oligomeric material；4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine ethanols and Material of the polyester mating type such as polyester compound of butanedioic acid etc., but it is not limited to these.As light stabilizer, in addition, also may be used To use known polymerism light stabilizer.
As the commercially available product of the light stabilizer, it can enumerate for example：TINUVIN 123、TINUVIN 152、TINUVIN 292 (BASF societies system, trade name, TINUVIN チ ヌ PVC Application be registration mark), HOSTAVIN 3058 (" Network ラ リ ア Application ト societies " System, trade name, Hostavin be registration mark), ア デ カ ス タ Block LA-82 (Asahi Denka Co., Ltd.'s system, trade name, ア デ カ ス タ Block ADKSTAB and ア デ カ ス タ Block be registration mark) etc..
In the case that coating composition (1) contains above-mentioned light stabilizer, the use level of the light stabilizer is relative to the coating In the range of the nonvolatile component total amount of composition (1), preferably 0.5~10 mass %, more preferably 0.8~9 mass % enters One step is preferably 1.0~8 mass %.
Coating composition (1) can be also containing the polymerizable unsaturated compound beyond the composition (A) and (B).As Polymerizable unsaturated compound beyond mentioned component (A) and (B) has 1 polymerism insatiable hunger it is preferable to use 1 intramolecular With the compound of group.
As the polymerizable unsaturated compound beyond mentioned component (A) and (B), it can enumerate for example：Monohydric alcohol and (first Base) carboxylate of acrylic acid, (methyl) acrylate of hydroxyl, (methyl) acrylate containing glycidyl, containing carboxyl (methyl) acrylate, vinyl aromatic compounds, containing azanyl (methyl) acrylate, polymerizable amide compound, Hydrolysable silanes compound with polymerism unsaturated group etc..
Wherein, the preferred carboxylate of monohydric alcohol and (methyl) acrylic acid, (methyl) acrylate of hydroxyl, carboxylic (methyl) acrylate, containing azanyl (methyl) acrylate.
As monohydric alcohol and the carboxylate of (methyl) acrylic acid, it can enumerate for example：(methyl) methyl acrylate, (methyl) third Olefin(e) acid ethyl ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) propylene Sour isobutyl ester, (methyl) tert-butyl acrylate, (methyl) acrylic acid peopentyl ester, (methyl) cyclohexyl acrylate, (methyl) propylene Sour tetrahydro furfuryl ester, (methyl) isobornyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, N- acryloyls Epoxide ethyl hexahydro phthalic amide etc..
As (methyl) acrylate of hydroxyl, it can enumerate for example：(methyl) Hydroxyethyl Acrylate, (methyl) propylene Sour hydroxy propyl ester, (methyl) hydroxy butyl acrylate etc..
As carboxylic (methyl) acrylate, it can enumerate for example：Acrylic acid, methacrylic acid, crotonic acid, clothing health Acid, maleic acid, fumaric acid, (methyl) acrylic acid 2- carboxyethyls, (methyl) acrylic acid 2- carboxyls propyl ester, (methyl) acrylic acid 5- Carboxyl pentyl ester etc..
As (methyl) acrylate containing glycidyl, it can enumerate for example：(methyl) glycidyl acrylate, alkene Propylglycidyl base ether etc..
As vinyl aromatic compounds, it can enumerate for example：Styrene, α-methylstyrene, vinyltoluene, α-chlorine Styrene etc..
As containing azanyl (methyl) acrylate, it can enumerate for example：N, N- dimethyl aminoethyl (methyl) acrylic acid Ester, N, N- diethylaminos ethyl (methyl) acrylate, N- t-butylamino ethyls (methyl) acrylate, 4- (methyl) third Enoyl- morpholine etc..
As polymerizable amide compound, it can enumerate for example：Acrylamide, Methacrylamide, N- methyl (methyl) third Acrylamide, N- ethyls (methyl) acrylamide, N- methoxies (methyl) acrylamide, N- butoxymethyls (methyl) propylene Acid amides, N, N- dimethyl (methyl) acrylamide, N, N- dimethylaminopropyls (methyl) acrylamide, N, N- dimethylaminos Ethyl (methyl) acrylamide, N- hydroxymethyls (methyl) acrylamide, N- (2- hydroxyethyls) (methyl) acrylamide etc..
As the hydrolysable silanes compound with polymerism unsaturated group, it can enumerate for example：3- (methyl) acryloyl Epoxide propyl trimethoxy silicane, 2- (methyl) acryloyl-oxyethyls trimethoxy silane, 3- (methyl) acryloxy third Ethyl triethoxy silicane alkane, 2- (methyl) acryloyl-oxyethyls triethoxysilane, 3- (methyl) acryloxypropyl Dimethoxysilane, trimethoxyvinyl silane, Triethoxyvinylsilane etc..
Coating composition (1) further can suitably contain crosslinking agent, solvent, pigment, catalyst, anti-oxidant as needed Agent, surface conditioner, defoamer, emulsifying agent, surfactant, anti-fouling agent, wetting agent, tackifier, dyestuff, marresistance are improved Commonly used other adding ingredients etc. in the fields of application such as agent, gloss regulator.
As above-mentioned crosslinking agent, for example the composition (A) and (B) it is at least one kind of there is hydroxyl in the case of, can make With the polyisocyanate compound (b1), blocked polyisocyanate compound, melmac etc., in mentioned component (A) and (B) it is at least one kind of have carboxyl in the case of, carbodiimide compound etc. can be used.
As the solvent, such as can use organic solvent, water.As the organic solvent, it can enumerate for example：Third The ketones such as ketone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK)；Ethyl acetate, butyl acetate, methyl benzoate, ethoxyl ethyl propionate, The esters such as ethyl propionate, methyl propionate；The ethers such as tetrahydrofuran, dioxanes, dimethoxy-ethane；Ethylene glycol single methyl ether, second The glycol ethers such as glycol list ethylether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3- methoxybutyl acetates Class；Aromatic hydrocarbon, aliphatic hydrocarbon etc..
Be explained, coating composition (1) be nonvolatile component account for 90~100 mass %, preferably 95~100 mass %, The Coating material composition of more preferably 98~100 mass %, so-called no-solvent type coating, preferably active energy ray curable Thing.
As the pigment, it can enumerate for example：Bright pigment, coloring pigment, extender pigment etc..The pigment can be single Solely use or two or more combines and used.
As the bright pigment, it can enumerate for example：Aluminium (also comprising AM aluminum metallization), copper, zinc, brass, nickel, glass thin Piece, aluminum oxide, mica, the aluminum oxide coated with titanium oxide and/or iron oxide, coated with titanium oxide and/or iron oxide Mica etc..
As the coloring pigment, it can enumerate for example：Titanium oxide, zinc oxide, carbon black, chrome vermillion, Prussian blue, cobalt blue, idol Nitrogen series pigments, phthualocyanine pigment, quinacridone pigment, isoindoline series pigments, intellectual circle's series pigments, perylene pigment, dioxanes Series pigments, diketopyrrolo-pyrrole series pigments, the hot pigment of screening etc..
As the extender pigment, it can enumerate for example：Clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talcum, two Silica, aluminum oxide are white etc..
Then, process (2) is illustrated.
Process (2) in the coating film-forming methods of the present invention is the coating composition (1) that will be prepared in the process (1) It is coated on the process on base material.
As the material of base material, it is not particularly limited, can is inorganic material or organic material or organic material and inorganic Any one of the mixing material of material.
As the inorganic material, it can enumerate for example：Iron, aluminium, brass, copper, tinplate, stainless steel, galvanized steel, kirsite The metal materials such as (such as Zn-Al, Zn-Ni, Zn-Fe) galvinized steel；Glass；Cement；Concrete etc..
As the organic material, it can enumerate for example：The acrylic resins such as polymethyl methacrylate, poly terephthalic acid Glycol ester, PEN, poly terephthalic acid -1,4 cyclohexane dimethanol ester, polyethylene -1,2- hexichol oxygen The polyester resin of -4,4 '-dicarboxylic ester of base ethane, polybutylene terephthalate (PBT) or the like, with エ ピ コ ー ト (trade names： " oiling シ ェ Le エ Port キ シ (strain) " makes) etc. commercially available product be the epoxy resin of representative, polycarbonate resin, polyimides tree Fat, novolac resin, phenolic resin, acrylonitrile-butadiene-styrene (ABS) (ABS) resin, acrylonitrile-vinyl-styrene (AES) resin, acrylonitrile-styrene-acrylic ester (ASA) resin, vinyl chloride resin, permalon, polyurethane resin, Cellulose esters (such as tri acetyl cellulose, diacetyl cellulose, propionyl cellulose, bytyry cellulose, acetyl group third Atriacetyl cellulose, NC Nitroncellulose), polyamide, polystyrene (such as syndiotactic polytyrene), polyolefin it is (such as polypropylene, poly- Ethene, polymethylpentene), polysulfones, polyether sulfone, polyarylate, PEI, polyether-ketone, various fibre reinforced plastics materials (Fiber Reinforced Plastics：Hereinafter referred to as FRP material or referred to as FRP.) etc..
Wherein, as the material of base material, preferably vinyl chloride resin, acrylonitrile-butadiene-styrene (ABS) (ABS) resin, propylene Nitrile-ethylene-stryene (AES) resin, acrylonitrile-styrene-acrylic ester (ASA) resin and polycarbonate resin, it is especially excellent Select vinyl chloride resin.
In general, vinyl chloride resin is due to excellent in workability, therefore, the base material as article with complex shape Situation is relatively more, and in the case where being applicable the method for the present invention, its effect is further improved.In addition, base material is removed only by plane Can be the complicated shape for for example combining multiple planes and/or curved surface outside the simple shape constituted.It is particularly complicated In the case of shape, it is however generally that, the insufficient part of the easy adaptation for producing the film with being made up of coating composition, In the case of the method for being applicable the present invention, its effect is further improved.
In addition, for base material, for example can be in the inorganic material or the organic material or organic material and inorganic material Application bottom-coating, cation electrodeposition coating, middle painting coating or coating etc. on the materials such as the mixing material of material and it is advance Form priming coat, electrodeposition coating layer, floating coat or upper coating etc..
For base material, it is possible to use selected from corona treatment, Corona discharge Treatment, active energy beam processing, flame The method of at least one kind of physics in processing, explosive treatment, polishing etc. is handled (physical treatment).
In addition, the purposes of the coated article as the coating composition (1) of the application present invention, is not particularly limited, Ke Yilie Citing is such as：The outer plate portion of the car bodies such as passenger car, truck, motorcycle, bus；Bumper, central post, reflective mirror, door The interior exterior member of the automobiles such as handle, instrument face plate, architrave, central control board；The families such as chair, vanity mirror, window frame, gate Has construction material associated member；Outer plate portion of the domestic electrical product such as portable phone, audio frequency apparatus etc..
The method that coating composition (1) is coated on base material is not particularly limited.Aerial spraying, nothing can for example be utilized Aerial spraying, rotary-atomizing coating machine, dipping coating, application member, bristle, roller etc. are coated.During coating, electrostatic can be carried out Apply.For coating film thickness, can with solidify thickness be set to usual 10~100 μm, preferably 10~70 μm, further preferred 10 In the range of~40 μm.
It is explained, coating composition (1) is preferably directly coated on base material.
In process (2) in the coating film-forming methods of the present invention, it is characterised in that in the implementation of process (2), with coating The interface of the base material of composition (1) contact reaches the temperature in the range of 28~70 DEG C.It is assumed that passing through the process (2), coating Carbamate (methyl) acrylate (A) and polymerizable unsaturated compound (B) in composition (1), particularly molecular weight It is impregnated with than relatively low polymerizable unsaturated compound (B) compared to substrate surface to inside, in process (3) below, the leaching Carbamate (methyl) acrylate (A) and polymerism on saturating polymerizable unsaturated compound (B) and substrate surface are not Saturated compounds (B) is polymerize and forms cured coating film, therefore, the excellent adhesion of base material and film.
Here, " in the implementation of process (2) " refers to：" from the moment of beginning applied coating composition (1) to coating composition (1) between coating terminates ".
The interface of base material for making to contact with coating composition (1) reaches the side of the temperature in the range of 28~70 DEG C Method, can specifically enumerate following method.
(a) before applied coating composition (1), the surface (interface) of the base material of applied coating composition (1) is heated, The surface of the base material is set to reach temperature in the range of 28~70 DEG C.Thereafter, coating composition (1) is coated on base material.Give To illustrate, at the time of coating composition (1) is contacted with base material, if the interface of the base material is in 28~70 DEG C of scope, The effect of the present invention can be produced.Accordingly, with respect to after coating composition (1) is coated on base material, by the base material The temperature at interface maintains the time of the temperature range, be it is arbitrary, for example, 2 seconds~60 seconds or so.In addition, during coating Such as preferably 35~60 DEG C of the temperature of coating composition (1).
(b) base material surface coating heating coating composition (1), the interface of the base material is reached 28~70 DEG C of model Enclose interior temperature.The temperature of coating composition (1) can for example be set to 28~70 DEG C, preferably 30~60 DEG C, more preferably 30~50 In the range of DEG C.
(c) before applied coating composition (1), the surface of the base material of applied coating composition (1) is heated, and In the coating composition (1) of the surface coating heating of base material, the interface of the base material is set to reach temperature in the range of 28~70 DEG C.
It is explained, in the above method (a)~(c), the coating composition (1) for being coated on the surface of base material is uncured State.
As the heating means in the above method (a)~(c), method well known in the art can be suitably used.Specifically For, it can use such as Hot-blast Heating, infrared heating, high-frequency heating.
In the present invention, preferred methods described (a), (b) or (c), further preferred method (a) or (b).Method (a) enters one The reasons why walking preferred can enumerate：The temperature at the interface of the base material rises in a short time；Due to process (2) implementation when anaplasia It is short, therefore, cause the possibility step-down of the surface defect of film；Can be without preparing special device in the heating of base material With regard to the simple method such as rising the temperature in base material safe-deposit vault can be made, therefore it is low cost；Deng.Method (b) is further excellent The reasons why selecting can enumerate：Can be without preparing special device with regard to such as coating machine or coating can be carried out in the heating of base material The simple method such as the firing equipment importing of tank, therefore be low cost etc..In the present invention, particularly preferred method (a).
In the present invention, in the implementation of process (2), the interface of the base material contacted with coating composition (1) preferably reaches 28~ Temperature in the range of 60 DEG C, further preferably reaches the temperature in the range of 28~50 DEG C.
Then, process (3) is illustrated.
Process (3) in the coating film-forming methods of the present invention is makes the coating on the base material being coated with the process (2) The process of composition (1) solidification.
, can be to the coating in the case that the polymerization initiator (C) is Photoepolymerizationinitiater initiater (C1) in process (3) Composition (1) irradiates active energy beam, solidifies the coating composition (1) on be coated with base material.
[active energy beam irradiation]
As illuminated active energy beam, known active energy beam can be used.Specifically, Ke Yilie Lift：Ultraviolet, visible rays, laser (near infrared ray laser, visual ray laser, ultraviolet laser etc.), microwave, electron beam, electricity Magnetic wave etc..In these active energy beams, from the viewpoint of economy, preferred ultraviolet.
The irradiation of active energy beam can use the arbitrary light source for the electromagnetic wave for sending following wavelength and carry out, described The light that the electromagnetic wave of wavelength can be absorbed in the coating composition (1) on the base material for being present in and being coated with the process (2) gathers Close initiator (C1).This light source generally sends the electromagnetic wave of wavelength 200nm~2,000nm scope.
As the irradiation source of active energy beam, known irradiation source can be used.Specifically, it can use and for example surpass High pressure, high pressure, middle pressure, the mercury vapor lamp of low pressure, electrodeless lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, Tungsten lamp, LED (Light Emitting Diode, light emitting diode), sunshine etc..Alternatively, it is also possible to use pulsed illumination type Active energy beam irradiation unit.
In addition, the irradiation of active energy beam can be carried out to Zone Full and/or for example via mask to a part, can To be carried out using laser beam.The solidification of the film in only specific region can also be carried out by the means.
For the exposure of active energy beam, generally, such as in the case of high-pressure mercury-vapor lamp, preferably 50~3, 000mJ/cm2In the range of, in the case of metal halide lamp, preferably 100~5,000mJ/cm2In the range of, it is particularly high In the case of medium pressure mercury lamp, preferably 100~1,000mJ/cm2In the range of, in the case of metal halide lamp, it is preferably 500~2,000mJ/cm2In the range of.The irradiation of active energy beam can be carried out in atmosphere or under inert gas.As Inert gas, can use nitrogen, carbon dioxide, argon, helium etc. or their mixture.
In addition, with solidifying caused by active energy beam simultaneously, can be heated.As heater meanses, it can use Such as hot blast, hot gas, infrared heater, IR radiators, baking oven, hot-rolling and microwave.In the case of being heated, from life Heating condition is determined from the viewpoint of heat endurance of yield, operability and base material etc., but heating-up temperature is 30~120 DEG C, In the range of particularly preferably 50~90 DEG C, the heat time is in the range of 1~60 minute, particularly preferably 1~20 minute.
In the case of being heated, the order of active energy beam irradiation and heating is not particularly limited, can be in activity Heated after energy-ray irradiation, active energy beam irradiation can also be carried out after heating, can also be carried out simultaneously Active energy beam irradiates and heated.
In addition, when carrying out active energy beam irradiation and heating at the same time, can be by the irradiation from active energy beam The heat (heat that such as lamp is sent) in source is as thermal source.And then, when carrying out active energy beam irradiation after heating, it is coated with The base material of feed composition can carry out active energy beam irradiation under the state (state with waste heat) with heat.
In addition, in the case that the polymerization initiator (C) is thermal polymerization (C2), by by the coating composition (1) heated, can solidify the coating composition (1) on be coated with base material.
[heating]
Heating can suitably use method well known in the art.Specifically, can use for example hot blast, hot gas, Infrared heater, IR radiators, baking oven, hot-rolling and microwave etc. and carry out.In the present invention, from the easiness of operation and can be with The viewpoint such as progress is set out at low temperature, is heated preferably by hot blast, infrared heater etc..
The viewpoints such as the heat endurance from productivity ratio, operability and base material, the temperature of the heating is preferably 30~150 In the range of DEG C, more preferably 40~140 DEG C, more preferably 50~130 DEG C.In addition, the time of the heating is preferably 1 In the range of~60 minutes, more preferably 1~40 minute.
[embodiment]
Hereinafter, Production Example, embodiment and comparative example are enumerated, the present invention is further specifically described.But, the present invention is not Limited by these.In each example, as long as no specified otherwise, " part " and " % " is based on quality criteria.In addition, the thickness base of film In cured coating film.
Each composition used in following examples is as described below.
[carbamate (methyl) acrylate (A)]
Carbamate (methyl) acrylate (A-1)：Weight average molecular weight is that 3,000, Tg is 40 DEG C, suitably selects above-mentioned (a1)~(a5) composition and make its react obtained from, 1 intramolecular there are average 2 acryloyl groups, 1 intramolecular there are 20 to be gathered The compound of oxy ethylene chain and 12 cyclohexane rings.
Carbamate (methyl) acrylate (A-2)：Weight average molecular weight is that 2,400, Tg is 26 DEG C, suitably selects above-mentioned (a1)~(a5) composition and make its react obtained from, 1 intramolecular there are average 2 acryloyl groups, 1 intramolecular there are 20 to be gathered The compound of oxy ethylene chain.
Carbamate (methyl) acrylate (A-3)：Weight average molecular weight is that 3,200, Tg is 45 DEG C, suitably selects above-mentioned (a1)~(a5) composition and make its react obtained from, 1 intramolecular there are average 2 acryloyl groups, 1 intramolecular to have 12 rings The compound of hexane ring.
Carbamate (methyl) acrylate (A-4)：Weight average molecular weight is that 2,600, Tg is 23 DEG C, suitably selects above-mentioned (a1)~(a5) composition and make its react obtained from, 1 intramolecular has average 2 acryloyl groups but 1 intramolecular is without poly- The compound of oxy ethylene chain and cyclohexane ring.
Carbamate (methyl) acrylate (A-5)：Weight average molecular weight is that 1,500, Tg is 37 DEG C, suitably selects above-mentioned (a1)~(a5) composition and make its react obtained from, 1 intramolecular there are average 3 acryloyl groups, 1 intramolecular there are 2 to be gathered The compound of oxy ethylene chain and 2 chlorinated isocyanurates rings.
Carbamate (methyl) acrylate (A-6)：Weight average molecular weight is that 1,400, Tg is 48 DEG C, suitably selects above-mentioned (a1)~(a5) composition and make its react obtained from, 1 intramolecular have average 3 acryloyl groups, 1 intramolecular have 2 it is different The compound of cyanurate ring.
Carbamate (methyl) acrylate (A-7)：Weight average molecular weight is that 850, Tg is 44 DEG C, suitably selects above-mentioned (a1)~(a5) composition and make its react obtained from, 1 intramolecular there are average 2 acryloyl groups, 1 intramolecular there are 2 to be gathered The compound of oxy ethylene chain and 4 cyclohexane rings.
Carbamate (methyl) acrylate (A-8)：Weight average molecular weight is that 9,800, Tg is 38 DEG C, suitably selects above-mentioned (a1)~(a5) composition and make its react obtained from, 1 intramolecular there are average 2 acryloyl groups, 1 intramolecular there are 80 to be gathered The compound of oxy ethylene chain and 42 cyclohexane rings.
[polymerizable unsaturated compound (B)]
Polymerizable unsaturated compound (B-1)：" ラ イ ト ア Network リ レ ー ト 3EG-A " (chemistry society of common prosperity society system, three second two Alcohol diacrylate, weight average molecular weight 258, polymerism unsaturated group number 2).
Polymerizable unsaturated compound (B-2)：" HDDA " (trade name, " ダ イ セ Le オ Le ネ Network ス societies " system, 1,6- Hexanediyl ester, weight average molecular weight 226, polymerism unsaturated group number 2).
Polymerizable unsaturated compound (B-3)：" Irr214K " (trade name, " ダ イ セ Le オ Le ネ Network ス societies " system, Tricyclodecane Dimethanol diacrylate, weight average molecular weight 300, polymerism unsaturated group number 2)
Polymerizable unsaturated compound (B-4)：" ニ ュ ー Off ロ Application テ ィ ア HPN " (trade name, the first industrial pharmaceutical society System, 3-hydroxypivalic acid neopentylglycol diacrylate, weight average molecular weight 312, polymerism unsaturated group number 2)
Polymerizable unsaturated compound (B-5)：" ア ロ ニ ッ Network ス M-315 " (trade name, East Asia synthesis society system, isocyanide urine Acid ethylene-oxide-modified two and triacrylate, weight average molecular weight 387, polymerism unsaturated group number 3)
Polymerizable unsaturated compound (B-6)：" SR230 " (trade name, " サ ー ト マ ー societies " system, propylene of diethylene glycol two Acid esters, weight average molecular weight 212, polymerism unsaturated group number 2)
Polymerizable unsaturated compound (B-7)：" NK エ ス テ Le A-400 " (trade name, chemical industry society of Xin Zhong villages system, Polyethylene glycol #400 diacrylates, weight average molecular weight 508, polymerism unsaturated group number 2)
[polymerization initiator (C)]
Polymerization initiator (C-1)：" IRGACURE 907 " (trade name, BASF societies system, Photoepolymerizationinitiater initiater, it is non-volatile into Divide containing ratio 100%)
Polymerization initiator (C-2)：" IRGACURE TPO " (trade name, BASF societies system, Photoepolymerizationinitiater initiater, it is non-volatile into Divide containing ratio 100%)
Polymerization initiator (C-3)：" パ ー オ Network タ O " (trade name, You societies system, thermal polymerization, nonvolatile component Containing ratio 100%)
Embodiment 1
[manufacture of coating composition (1)]
In the mixing ratio (mass parts) shown in table 1 below, various composition is mixed, coating composition is prepared (1).I.e.：
By 40 parts of carbamate (methyl) acrylate (A-1) (40 parts of nonvolatile component),
20 parts of polymerizable unsaturated compound (B-1) (20 parts of nonvolatile component),
10 parts of polymerizable unsaturated compound (B-2) (10 parts of nonvolatile component),
20 parts of polymerizable unsaturated compound (B-3) (20 parts of nonvolatile component),
" ACMO " (trade name, " KJ ケ ミ カ Le ズ societies " system, 4- acryloyl morpholines, weight average molecular weight 141, polymerism are not Saturated group number 1) 10 parts (10 parts of nonvolatile component),
Polymerization initiator (C-1) " IRGACURE 907 " (trade name, BASF societies system, Photoepolymerizationinitiater initiater, nonvolatile component Containing ratio 100%) 5 parts,
Polymerization initiator (C-2) " IRGACURE TPO " (trade name, BASF societies system, Photoepolymerizationinitiater initiater, nonvolatile component Containing ratio 100%) 1 part,
" TINUVIN 400 " (trade name, BASF societies system, triazine system ultra-violet absorber, nonvolatile component containing ratio 100%) 2 parts,
" TINUVIN292 " (trade name, BASF societies system, amine system of being obstructed light stabilizer, nonvolatile component containing ratio 100%) 2 Part and
" BYK-333 " (trade name, " PVC ッ Network ケ ミ ー societies " system, silicon systems surface conditioner, nonvolatile component containing ratio 100%) 0.1 part equably mixes, and obtains coating composition (1).
(note 1) ACMO：Trade name, " KJ ケ ミ カ Le ズ societies " system, 4- acryloyl morpholines, weight average molecular weight 141, polymerization Property unsaturated group number 1.
(note 2) HEAA：Trade name, " KJ ケ ミ カ Le ズ societies " system, N- (2- hydroxyethyls) acrylamide, weight average molecular weight 115th, polymerism unsaturated group number 1.
(note 3) IBOA-B：Trade name, " ダ イ セ Le オ Le ネ Network ス societies " system, isobornyl acrylate, Weight-average molecular Amount 208, polymerism unsaturated group number 1.
(note 4) β-CEA：Trade name, " ダ イ セ Le オ Le ネ Network ス societies " system, β-acryloxypropionic acid, Weight-average molecular Amount 144, polymerism unsaturated group number 1.
(note 5) polymerization initiator (C-4)：" (trade name, Japanese chemical drug society system, photopolymerization trigger KAYACURE DETX-S " Agent, nonvolatile component containing ratio 100%)
[making of breadboard]
100mm × 150mm × 3.0mm vinyl chloride base material (PVC) is heated to after 50 DEG C, stood at 23 DEG C, is used Non-contact thermometer " THERMO-HUNTER PT-80 " (OPTEX societies system, trade name, the carrying of long range Narrow Field Of Vision measure type Type non-contact thermometer) the METHOD FOR CONTINUOUS DETERMINATION vinyl chloride base material surface temperature.Turn into 30 in the surface temperature of the vinyl chloride base material DEG C when, on the vinyl chloride base material using bar coater by the thickness of cured coating film turn into 15 μm in the way of application be maintained at painting material temperature The coating composition (1-1) obtained in the Production Example 1 of 23 DEG C of degree.Then, carry out solidifying for 1 minute at 23 DEG C, thereafter, use gold Belong to halide lamp and carry out 400mW/cm2、1,000mJ/cm2UV irradiation, make breadboard.
[evaluation of breadboard]
To obtained each breadboard, various experiments are carried out.Evaluation result is shown in table 1.
(test method)
Adaptation：2mm × 2mm gridiron pattern is made according to JIS K 5600-5-6 (1990) on the painting face of each breadboard 100, the Continuous pressing device for stereo-pattern on the face is studied the survivor state of the gridiron pattern film after sharp peeling, commented by following benchmark Valency tack.
◎：Remaining number/entirety number=100/100, intact side
○：Remaining number/entirety number=100/100, there is scarce side
△：Remaining number/entirety number=90~99/100
Pencil hardness：The painting face of each breadboard is determined according to JIS K 5600-5-4 (1999) " stretching hardness (pencil method) " Pencil hardness.If pencil hardness is more than HB, hardness is good.
Embodiment 2~9
Change carbamate (methyl) acrylate (A) and the unsaturated chemical combination of other polymerisms like that as shown in table 1 The species of thing, in addition, repeats embodiment 1.Show the result in table 1.
[table 1]
Embodiment 10~18
Change the kind of polymerizable unsaturated compound (B) and other polymerizable unsaturated compounds like that as shown in table 2 Class, in addition, repeats embodiment 1.Show the result in table 2 and 3.
[table 2]
Embodiment 19~21
Change the surface temperature of base material like that as shown in table 3, in addition, repeat embodiment 1.Show the result in table 3.
[table 3]
Table 3 (mass parts)
Embodiment 22~26
Adjust the amino when nonvolatile component of coating composition (1) to be set to total 100 mass parts like that as shown in table 4 The nonvolatile component of formic acid esters (methyl) acrylate (A) and nonvolatile component, the others of polymerizable unsaturated compound (B) Nonvolatile component in polymerizable unsaturated compound or coating composition (1), in addition, repeats embodiment 1.By result It is shown in table 4.
[table 4]
Embodiment 27~30
Omit the heating of base material in embodiment 1, the temperature of coating composition (1) changed such as table 5, it is as shown in table 5 that The surface temperature of base material in sample adjustment process (2), in addition, repeats embodiment 1.Show the result in table 5.
[table 5]
Table 5 (mass parts)
Embodiment 31
Heat 30 minutes to come at 80 DEG C except polymerization initiator and progress is changed like that as shown in table 6 in embodiment 1 Instead of carrying out outside the UV irradiations using metal halide lamp, embodiment 1 is repeated.Show the result in table 6.
[table 6]
Table 6 (mass parts)
Comparative example 1~4
Change the species of carbamate (methyl) acrylate (A) like that as shown in table 7, in addition, repeat to implement Example 1.Show the result in table 7.
Compare composition (a1)=carbamate (methyl) acrylate：Weight average molecular weight is that 2,900, Tg is 40 DEG C, fitted When selection above-mentioned (a1)~(a5) composition and obtained from being reacted, 1 intramolecular there is average 1 acryloyl group, 1 intramolecular Compound with 20 polyethylene oxide chains and 12 cyclohexane rings.
Compare composition (a2)=carbamate (methyl) acrylate：Weight average molecular weight be 490, Tg be 42 DEG C, it is appropriate Selection above-mentioned (a1)~(a5) composition and obtained from being reacted, 1 intramolecular there is average 2 acryloyl groups, 1 intramolecular tool There is the compound of 2 cyclohexane rings.
Compare composition (a3)=carbamate (methyl) acrylate：Weight average molecular weight is that 11,000, Tg is 29 DEG C, fitted When selection above-mentioned (a1)~(a5) composition and obtained from being reacted, 1 intramolecular there are average 2 acryloyl groups, 1 intramoleculars Compound with 128 polyethylene oxide chains and 32 cyclohexane rings.
[table 7]
Table 7 (mass parts)
Comparative example 5~8
Change polymerizable unsaturated compound (B) species like that as shown in table 8, in addition, repeat embodiment 1.Will As a result it is shown in table 8.
Compare composition (b1)=polymerizable unsaturated compound：" EBECRYL110 " (trade name, " ダ イ セ Le オ Le ネ Network ス societies " system, ethoxylation phenyl acrylate (EO2 moles), weight average molecular weight 236, polymerism unsaturated group number 1)
Compare composition (b2)=polymerizable unsaturated compound：" SR213 " (trade name, " サ ー ト マ ー societies " system, 1,4- Butanediol diacrylate, weight average molecular weight 198, polymerism unsaturated group number 2)
Compare composition (b3)=polymerizable unsaturated compound：" NK エ ス テ Le A-DPH " (trade name, Xin Zhong villages chemistry Industrial society's system, dipentaerythritol acrylate, weight average molecular weight 578, polymerism unsaturated group number 6)
[table 8]
Table 8 (mass parts)
Comparative example 9~11
Change the surface temperature of base material like that as shown in table 9, in addition, repeat embodiment 1 or 21.Show the result in table 9。
[table 9]
Table 9 (mass parts)
Embodiment 32~35
Change the material of base material like that as shown in table 10, in addition, repeat embodiment 1.Show the result in table 10.
ABS=acrylonitrile-butadiene-styrene (ABS)s
AES=acrylonitrile-vinyls-styrene
ASA=acrylonitrile-styrene-acrylic esters
PC=makrolon
[table 10]
Table 10 (mass parts)
Embodiment 36~39
Change the thickness of cured coating film like that as shown in table 11, in addition, repeat embodiment 1.Show the result in table 11.
[table 11]
Table 11 (mass parts)
Embodiment 40~44
Change polymerizable unsaturated compound (B), polymerization initiator (C) and other polymerisms like that as shown in table 12 not The species of saturated compounds, in addition, repeats embodiment 1.Show the result in table 12.
[table 12]
Table 12 (mass parts)
As can be known from the above results：In embodiment, due to all meeting process (1)~(3) specified in the present invention Condition, therefore, it can to form the excellent adhesion with base material and the film with high intensity.On the other hand, in a comparative example, Due to be unsatisfactory for process specified in the present invention (1)~(3) condition it is any, it is thus impossible to produce the effect above.

Claims (10)

1. a kind of coating film-forming methods, it is characterised in that have：
Process (1)：Prepare the process of coating composition (1), the coating composition (1) is more than 550 containing weight average molecular weight And be less than in the range of 10,000 and carbamate (methyl) third of 1 intramolecular with more than 2 (methyl) acryloyl group Olefin(e) acid ester (A), weight average molecular weight are 200 less than in the range of 550 and 1 intramolecular has the polymerism of more than 2 not The polymerizable unsaturated compound (B) and polymerization initiator (C) of saturated group；
Process (2)：The coating composition (1) prepared in the process (1) is coated on to the process on base material；
Process (3)：The process for solidifying the coating composition (1) on the base material being coated with the process (2), wherein
In the implementation of the process (2), the interface of the base material contacted with the coating composition (1) reaches 28 to 70 DEG C In the range of temperature.
2. coating film-forming methods according to claim 1, wherein, the coating composition (1) is containing weight average molecular weight 550 less than in the range of 10,000 and 1 intramolecular has (methyl) acryloyl group of more than 2 and more than 1 is gathered Carbamate (methyl) acrylate (A11) of alkylidene oxide chain is used as the carbamate (methyl) acrylate (A) at least its a kind.
3. coating film-forming methods according to claim 1 or 2, wherein, the coating composition (1) contains weight average molecular weight For 550 less than in the range of 10,000 and 1 intramolecular have more than 2 (methyl) acryloyl group and more than 1 Carbamate (methyl) acrylate (A12) of cyclohexane ring is used as the carbamate (methyl) acrylate (A) At least its a kind.
4. coating film-forming methods according to any one of claim 1 to 3, wherein, the coating composition (1) contains weight Average molecular weight is 550 less than in the range of 10,000 and 1 intramolecular has (methyl) acryloyl group and 1 of more than 2 Carbamate (methyl) acrylate (A13) of chlorinated isocyanurates ring more than individual is used as the carbamate (methyl) third At least its a kind of olefin(e) acid ester (A).
5. coating film-forming methods according to any one of claim 1 to 4, wherein, the coating composition (1) contains tool Have the polymerizable unsaturated compound (B ') of polyoxyalkylene chain as the polymerizable unsaturated compound (B) at least its 1 kind.
6. coating film-forming methods according to any one of claim 1 to 5, wherein, for the coating composition (1), When being set to amount to 100 mass parts by the nonvolatile component of the coating composition (1), carbamate (methyl) acrylic acid Ester (A) is 10 to 80 mass parts, and the polymerizable unsaturated compound (B) is 20 to 90 mass parts.
7. coating film-forming methods according to any one of claim 1 to 6, wherein, in the coating composition (1), no Volatile ingredient accounts for 90 to 100 quality %.
8. coating film-forming methods according to any one of claim 1 to 7, wherein, the process (2) is in advance will be with institute The interface for stating the base material of coating composition (1) contact is heated to after the temperature in the range of 28 to 70 DEG C, is applied described Feed composition (1) is coated on the process on the base material.
9. coating film-forming methods according to any one of claim 1 to 8, wherein, the process (2) is to be advance by described in Coating composition (1) is heated to after the temperature in the range of 28 to 70 DEG C, and the coating composition (1) is coated on into the base material On process.
10. coating film-forming methods according to any one of claim 1 to 9, wherein, in the process (3), described poly- Initiator (C) is closed in the case of Photoepolymerizationinitiater initiater (C1), active energy beam is irradiated to the coating composition (1), In the case that the polymerization initiator (C) is thermal polymerization (C2), the coating composition (1) is heated.
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