CN102167942B - For the silane coupling agent with inorganic thin film plastics, band inorganic thin film plastics, mould internal shaping decorating film and insert part forming decorating film - Google Patents
For the silane coupling agent with inorganic thin film plastics, band inorganic thin film plastics, mould internal shaping decorating film and insert part forming decorating film Download PDFInfo
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- 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
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- 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
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/60—Additives non-macromolecular
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Abstract
The invention provides a kind of novel silane coupling agent of the plastics for the manufacture of band inorganic thin film, it touches with inorganic thin film and plastic basis material, even and if the plastics with inorganic thin film are at high temperature processed also can not produce on inorganic thin film face can be judged by visual crackle, interference fringe and obvious albefaction position.It is the silane coupling agent that the acrylic copolymer of-5 ~ 120 DEG C and (B) at least have the polyaziridine compound of 3 aziridinyls that its use comprises second-order transition temperature that (A) have carboxylate anion's group.
Description
Technical field
The present invention relates to a kind of for making inorganic thin film layer and the closely sealed silane coupling agent of plastic basis material, plastics, mould internal shaping decorating film and insert part forming decorating film with inorganic thin film.
Background technology
All the time, by plastic basis material surface coated silane coupling agent and and then the composite base material forming the inorganic thin film that is made up of aluminium, tin etc. and obtain (hereinafter referred to as band inorganic thin film plastics) according to the difference forming the kind of material of inorganic thin film and thickness etc., the wrapping material such as bottle, lid and gas barrier film, transparent conductive sheets, film capacitor etc. can be preferably used as.In addition, in membranaceous band inorganic thin film plastics, there are the plastics of the very thin aluminium lamination of tens of about nm, be widely used as decorating film (also referred to as transfer foil) especially and use component.
But, for band inorganic thin film plastics, regardless of its form, all deposit the problem at high temperature producing albefaction position in inorganic thin film face.In addition, when being with inorganic thin film plastics to be membranaceous, when hot conditions formed machining, not only can produce albefaction position on the inorganic thin film face of non-processing department, also can produce interference fringe and the crackle of range estimation with regard to judging on the inorganic thin film face of working position, the technical feature (gas barrier property, electromagnetic wave shielding performance etc.) that infringement inorganic thin film possesses and designability.
About crack problem, known such as in patent documentation 1, can be solved by the three liquid type silane coupling agents containing acrylic resin, melamine resin and polyisocyanate compounds, but do not mention albinism.In addition, as the base resin of silane coupling agent, sometimes also use urethane resin or vibrin, but when using the silane coupling agent made like this, the bad order in inorganic thin film face, in addition, is also difficult to eliminate the above-mentioned problem such as albefaction, crackle.
[background technology document]
[patent documentation]
[patent documentation 1] Japanese Unexamined Patent Publication 2004-122456 publication
Summary of the invention
Problem of the present invention is, a kind of novel silane coupling agent of the plastics for the manufacture of band inorganic thin film is provided, it touches with inorganic thin film and plastic basis material, even and if band inorganic thin film plastics are at high temperature processed also can not produce on inorganic thin film face can be judged by visual crackle, interference fringe and obvious albefaction position.
The present inventor is through repeatedly furtheing investigate, found that, the second-order transition temperature that utilization comprises (A) has carboxylate anion's group is the band inorganic thin film plastics silane coupling agent that the acrylic copolymer of-5 ~ 120 DEG C and (B) at least have the polyaziridine compound of 3 aziridinyls, can solve above-mentioned problem.
Utilize silane coupling agent of the present invention, level and smooth inorganic thin film can be formed on plastic basis material surface.In addition, when inorganics is metal, the gloss of inorganic thin film is excellent.In addition, inorganic thin film and plastics can be made to touch well.
In addition, even if the band inorganic thin film plastics obtained by silane coupling agent of the present invention are also difficult in inorganic thin film face produce albefaction position (following, this effect to be called " whitening resistance ") under the high temperature conditions.Particularly film material, even if form processing in high temperature environments, inorganic thin film is also difficult to produce and (this effect is called " resist processing " below by estimating crackle, interference fringe and the albefaction position that can judge.)。
Therefore, band inorganic thin film plastics of the present invention except useful in the exercise uses such as the wrapping material such as bottle, bottle cap and gas barrier film, transparent conductive sheets, film capacitor, the component of the component being also preferably used as insert part forming decorating film and the mould internal shaping decorating film of at high temperature implementing formed machining.
Accompanying drawing explanation
Fig. 1 is the outward appearance (electron micrograph, 3000 times) that processibility is evaluated as the aluminium-vapour deposition film of 6.
Fig. 2 is the outward appearance (electron micrograph, 3000 times) that processibility is evaluated as the aluminium-vapour deposition film of 5.
Fig. 3 is the outward appearance (electron micrograph, 3000 times) that processibility is evaluated as the aluminium-vapour deposition film of 4.
Fig. 4 is the outward appearance (electron micrograph, 3000 times) that processibility is evaluated as the aluminium-vapour deposition film of 3.
Fig. 5 is the outward appearance (electron micrograph, 3000 times) that processibility is evaluated as the aluminium-vapour deposition film of 2.
Fig. 6 is the outward appearance (electron micrograph, 3000 times) that processibility is evaluated as the aluminium-vapour deposition film of 1.
Embodiment
Silane coupling agent of the present invention comprises the aziridinyl ring opening catalyst (C) (hereinafter referred to as (C) composition) that second-order transition temperature that (A) have carboxylate anion's group is the acrylic copolymer (hereinafter referred to as (A) composition) of-5 ~ 120 DEG C, polyaziridine compound (hereinafter referred to as (B) composition) that (B) at least has 3 aziridinyls and adds as required.
As (A) composition, as long as there is described second-order transition temperature and there is in molecule carboxylate anion's group (-COO
-) acrylic copolymer, just can use various known material and be not particularly limited.
As the preferred form of (A) composition, can enumerate the material of the multipolymer neutralization of other unsaturated monomer reaction making (a1) α, beta-unsaturated carboxylic acid (hereinafter referred to as (a1) composition), (a2) (methyl) alkyl acrylate and/or styrenic (hereinafter referred to as (a2) composition) and (a3) add as required.
As (a1) composition, such as, can enumerate α, β-unsaturated monocarboxylic acids such as vinylformic acid, methacrylic acid, β-crotonic acid, iso-crotonic acid; The monoesters etc. of α, β-unsaturated dicarboxylic acids such as fumaric acid, toxilic acid (acid anhydride) and this α, β-unsaturated dicarboxylic acid and various alcohol.
As (a2) composition, i.e. (methyl) alkyl acrylate, such as can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) lauryl acrylate, (methyl) octadecyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid ring pentyl ester, (methyl) isobornyl acrylate etc.It should be noted that, the alkyl of (a2) composition does not have the functional group containing reactive hydrogen such as hydroxyl.In addition, the carbonatoms of this alkyl is generally about 1 ~ 20, is preferably about 1 ~ 8, more preferably 1 ~ 5.In addition, as styrenic, such as, can enumerate vinylbenzene, alpha-methyl styrene, t-butyl styrene, dimethyl styrene etc.
As (a3) composition, such as can enumerate (methyl) acrylate, (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) dihydroxypropyl cyclohexyl, (methyl) vinylformic acid 4-(methylol) cyclohexylmethyl, 2 hydroxy propanoic acid 4-(methylol) cyclohexylmethyl, (methyl) crylic acid hydroxylphenyl ester, N-(2-hydroxyethyl) acrylamide, hydroxyl (methyl) esters of acrylic acids such as N-(1-methyl-2-hydroxyethyl) acrylamide, (methyl) acrylic amide, unsaturated sulfonic acid Class, aminoalkyl group system unsaturated monomer class, poly (oxyalkylene) base system unsaturated monomer class, chlorosilane system (methyl) esters of acrylic acid, (gathering) siloxanes list (methyl) esters of acrylic acid, fluoroalkyl (list) esters of acrylic acid etc.
(a1) use % by mole of composition and (a2) composition is not particularly limited, and is usually followed successively by about 7 ~ 70 % by mole, about 30 ~ 93 % by mole, is preferably about 13 ~ 45 % by mole, 55 ~ 87 % by mole.In addition, when using (a3) composition, (a1) use % by mole of composition ~ (a3) composition is followed successively by about 7 ~ 70 % by mole, about 29 ~ 92 % by mole, about 1 ~ 60 % by mole usually, is preferably 13 ~ 45 % by mole, 52 ~ 84 % by mole, 3 ~ 20 % by mole.
(A) manufacture method of composition is not particularly limited, such as can enumerate under the existence of polymerization starter and organic solvent, usually at about 80 ~ 180 DEG C, after described in making, (a1) composition ~ (a3) composition carries out the radical polymerization of 1 ~ 20 hours, the method polymkeric substance of gained neutralized with neutralizing agent.
As polymerization starter, benzoyl peroxide, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, 2 can be enumerated, 2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2,4-methyl pentane nitrile) etc.
As organic solvent, the ethers (not comprising the material suitable with ether-ether class described later) such as the alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, ethylene glycol (not comprising the material suitable with ether-ether class with ether described later), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether can be enumerated; The ether-ether such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether class; The ketone such as acetone, methyl ethyl ketone; Dimethyl formamide etc.
As neutralizing agent, ammonia can be enumerated; The primary amine classes such as MMA, mono aminoethane, dibutyl amine, hexahydroaniline; The secondary amine such as dimethylamine, diethylamine class; The tertiary amines such as Trimethylamine 99, triethylamine; The alkali metal hydroxide such as sodium hydroxide, potassium hydroxide; The alkaline-earth metal oxyhydroxide etc. such as magnesium hydroxide.Wherein, when using tertiary amines and/or ammonia, the whitening resistance of tunicle and processibility, resistance to dissolubility etc. are good especially, therefore preferably.The carboxyl that the usage quantity of neutralizing agent has relative to acrylic copolymer, is generally the scope of about 80 ~ 300 % by mole.
Mainly from the viewpoint of whitening resistance and particularly processibility, the second-order transition temperature of (A) composition is-5 ~ 120 DEG C, preferably 40 ~ 110 DEG C.In addition, this second-order transition temperature is measured value.
(A) content of carboxylate anion's group of composition is not particularly limited, and is generally about 0.5 ~ 8mmol/g, is preferably 1 ~ 5mmol/g, and time within the scope of this, particularly whitening resistance and resist processing sexual orientation are in change well.In addition, so-called " content of carboxylate anion's group ", referring to the mole number of carboxylate anion's group contained in 1g (A) composition (being converted into nonvolatile component), is calculated value.
(A) weight-average molecular weight (the polystyrene conversion value obtained by gel permeation chromatography) of composition is also not particularly limited, main from the viewpoint of whitening resistance and processibility, be generally about 3000 ~ 100000, be preferably 10000 ~ 80000.
As (B) composition, as long as the material at least containing 3 aziridinyls in molecule, various known material (with reference to No. 4382135, United States Patent (USP), No. 2003-104970, Japanese Unexamined Patent Publication etc.) just can be used with no particular limitation.Specifically, preferably with the compound that following general formula represents.
(in formula, X
1represent hydrogen, the alkyl of carbonatoms 1 ~ 6 or the hydroxyalkyl of carbonatoms 1 ~ 3, R
1represent hydrogen or methyl, R
2and R
3represent the alkyl of hydrogen or carbonatoms 1 ~ 6 respectively.)
As the compound represented with this formula, tetramethylol methane-three-(β-aziridinyl propionic ester), trimethylolpropane tris (β-aziridinyl propionic ester) and glyceryl three (β-aziridinyl propionic ester) etc. can be enumerated.
As other (B) composition, four aziridine cpds etc. such as four aziridinyl m-xylene diamines, four aziridinyl methyl p dimethylamines, tetramethyl-propane four aziridinyl propionic ester can be enumerated.
In addition, can also by neopentyl glycol two (β-aziridinyl propionic ester), 4 together with (B) composition, 4 '-isopropylidenediphenol two (β-aziridinyl propionic ester), 4, two aziridine cpds and 2-methylaziridine, the 2-ethylaziridine, 2 such as 4 '-methylene radical biphenol two (β-aziridinyl propionic ester), single aziridine cpds such as 2-dimethylaziridine, 2,3-dimethylaziridine, 2-phenyl aziridine.
(B) content of the aziridinyl of composition is not particularly limited, and when especially considering whitening resistance and resist processing etc., is generally about 3 ~ 11mmol/g, preferably in the scope of 5 ~ 9mmol/g.In addition, so-called " content of aziridinyl ", referring to the mole number of aziridinyl contained in 1g (B) composition, is calculated value.
Particularly consider from the object making whitening resistance and resist processing improve, (C) composition can be used as required.As concrete example, the acid catalysts such as tosic acid, hydrochloric acid, bromic acid, acid iodide, fluoric acid, fluosulfonic acid, sulfuric acid, phosphoric acid and diaryl group iodized salt, triarylsulfonium salt, Er Fang Ji phosphonium salt etc. can be enumerated.Wherein, in order to easy process, preferred acid catalyzer, particularly preferably tosic acid.In addition, as required, above-mentioned neutralizing agent can be used together with (C) composition, preferably use ammonia.This neutralizing agent can use as the aqueous solution.
Silane coupling agent of the present invention utilizes various known method (A) composition, (B) composition and (C) composition of adding as required to be obtained by mixing.(A) the content ratio of composition and (B) composition is not particularly limited, particularly from the viewpoint of whitening resistance and resist processing, usually, [usage quantity (g) (being converted into nonvolatile component) of content (mmol/g) × (A) composition of carboxylate anion's group of (A) composition)/[usage quantity (g) (being converted into nonvolatile component) of content (mmol/g) × (B) composition of the aziridinyl of (B) composition] be generally about 0.01 ~ 10, preferably 0.1 ~ 2 scope.In addition, the usage quantity of (C) composition is not particularly limited, and usually, counts the scope of 1 ~ 15 about % by weight, preferably 5 ~ 10 % by weight relative to (B) composition with solids component conversion.
Silane coupling agent of the present invention can to use described organic solvent, water (ion exchanged water etc.) as the form of the solution of solvent.As this organic solvent, preferred above-mentioned alcohols.In addition, time with an organic solvent and both water, usual weight ratio is followed successively by about 9/1 ~ 1/9.
The nonvolatile component of silane coupling agent of the present invention is not particularly limited, and is generally 5 ~ 50 about % by weight.In addition, usually, in this nonvolatile component, (A) composition, (B) composition and the amount shared by (C) composition are followed successively by 42 ~ 85 about % by weight, 15 ~ 58 about % by weight and 0 ~ 8 about % by weight.
In silane coupling agent of the present invention, the additives such as other flow agent, antioxidant, UV light absorber, silica gel, filler can also be coordinated.
The layer that band inorganic thin film plastics of the present invention have plastic basis material, the layer formed by silane coupling agent of the present invention and formed by inorganic thin film.As plastic basis material, can enumerate polyester, polyvinyl chloride, polymeric amide, polyimide, polycarbonate, polyethylene, polypropylene etc., these compounds also can carry out the surface treatments such as corona discharge.
This plastic basis material is the structures (material except suitable with plastic film) or membranaceous such as spherical, cylindrical, rectangular-shaped, tabular, also can there is concavo-convex and curved surface in the local on surface.The thickness of membranaceous plastic basis material is not particularly limited, and is generally about 12 ~ 200 μm.
As the chemical substance forming inorganic thin film, can enumerate the metal oxide such as the metals such as aluminium, gold and silver, palladium, tin or aluminum oxide, stannic oxide, tin indium oxide, titanium oxide, silicon oxide, they can be used together.
The method manufacturing band inorganic thin film plastics of the present invention is not particularly limited, such as can enumerate after the various known method of silane coupling agent use of the present invention is coated on above-mentioned plastic basis material, make undercoat solidify (treatment condition: usual about 60 ~ 165 DEG C, 10 seconds ~ about 5 points), on base coating surface, then form the method for above-mentioned inorganic thin film kind.
As the coating process of silane coupling agent, spraying, roller coat, inverse print roll coating, intaglio plate coating, scraper for coating, rod painting, spot printing etc. can be enumerated.Glue spread is not particularly limited, and usually counts 0.01 ~ 10g/m with nonvolatile component
2left and right.
As the method forming inorganic thin film, various known physical method (vacuum thermal evaporation, sputtering etc.), chemical process (chemical gas phase reaction etc.) can be enumerated.In addition, the thickness of inorganic thin film is generally about 5 ~ 800nm.
Band inorganic thin film plastics of the present invention can also possess release layer, hard coat, hard coat immovable bed, various functional layer such as decorative pattern ink liquid layer, bond layer etc.
In band inorganic thin film plastics of the present invention, plastic basis material is the parts that membranaceous material (band inorganic thin film plastic film) is particularly useful for as mould internal shaping decorating film or insert part forming decorating film.Now, preferably this plastic basis material is polyester film, inorganic thin film layer is aluminium lamination and/or the tin layers of about 5 ~ 50nm.
Embodiment
Below, by embodiment and comparative example, the present invention is described in more details, but the present invention is not limited within the scope of this.In addition, " part " in embodiment represents weight standard.
In each example, second-order transition temperature is the value using commercially available determining instrument (goods name " DSC8230B ", motor of science (strain) are made) to record.In addition, number-average molecular weight uses commercially available gel permeation chromatograph device (manufacturing name " HLC-8220GPC ", eastern Cao (strain) system) to measure the value obtained.
The preparation > of < (A) composition
Production Example 1
To in the reaction vessel having whipping appts, thermometer, reflux exchanger, dropping funnel and nitrogen ingress pipe, add commercially available styrene acrylic copolymer containing carboxyl (goods name " ARUFON-UC3920 ", East Asia synthesis (strain) manufacture, nonvolatile component 100%, (a1) composition are vinylformic acid, (a2) composition be vinylbenzene) 500.0 parts, Virahol (hereinafter referred to as IPA) 150.0 parts, ion exchanged water (hereinafter referred to as IW) 2055.6 parts, 28% ammoniacal liquor (hereinafter referred to as 28%NH
3) 155.8 parts, 45 DEG C of insulations 3 hours, obtain second-order transition temperature (hereinafter referred to as Tg) be 104 DEG C, carboxylate anion's group content (hereinafter referred to as CA) is 4.3mmol/g, weight-average molecular weight (hereinafter referred to as Mw) is (A-1) composition of 15500 solution (nonvolatile component (hereinafter referred to as NV) is 20%).
Production Example 2
To in the reaction vessel identical with Production Example 1, add methacrylic acid (hereinafter referred to as MAA) 16.8 parts, methyl methacrylate (hereinafter referred to as MMA) 151.2 parts, HEMA (hereinafter referred to as 2-HEA) 72 parts, 2,2 '-azo two (methylbutyronitrile) (hereinafter referred to as ABN-E) 1.2 parts, IPA360 part, keep 5 hours (being pre-polymerization operation above) at 80 DEG C under nitrogen flowing.Then ABN-E2.4 part is added, by reaction system insulation 3 hours (being post polymerization operation above) further near uniform temp.Then, add IPA288.2 part, IW288.2 part, triethylamine (hereinafter referred to as TEA) 23.6 parts carry out neutralizing (above is neutralization, dilution operation).The physical property of (A-2) composition obtained thus is as shown in table 1.
Production Example 3 ~ 6, compare Production Example 1 ~ 3
Except using the raw material of number as shown in table 1, by the method identical with Production Example 2, the various solution of (AC-1) composition ~ (AC-3) composition obtaining (A-3) composition ~ (A-6) composition and compare.Each physical property is shown in table 1.
[table 1]
AA: vinylformic acid
BA: n-butyl acrylate
28%NH
3: 28% ammoniacal liquor
Relatively Production Example 4
To in the reaction vessel identical with Production Example 1, add terephthalic acid 479 parts, m-phthalic acid 402 parts, nonane diacid 87 parts, ethylene glycol 256 parts, 1,6-hexylene glycol 354 parts and glycerol 23 parts, stirring heating reaction system makes it dissolve.Then, water removing reaction system generated in dehydration condensation, meanwhile, utilizes 3 hours from 160 DEG C and is warming up to 200 DEG C, further 200 DEG C of insulations 1 hour.Then antimonous oxide 0.16 part is added.Then, reaction vessel is connected with vacuum decompression device, 235 DEG C, carry out decompression polycondensation 1 hour under 2.8kPa.Then, remove decompression state, reaction system is cooled to 150 DEG C, in reaction system, adds trimellitic acid 1,2-anhydride 119 parts, be incubated 1 hour.Next, add methyl iso-butyl ketone (MIBK) 1997 parts, methyl ethyl ketone 1997 parts make it uniform dissolution, obtain that Tg is 19 DEG C, the solution (NV is 35 % by weight) of CA to be 0.4mmol/g, Mw the be vibrin (PE-1) of 30000.
Relatively Production Example 5
To in the reaction vessel identical with Production Example 1, add commercially available polycarbonate diol (goods name " ニ Star Port ラ Application 980R ", number-average molecular weight 2000; Nippon Polyurethane Industry (Ltd.)) 362.3 parts, isophorone diisocyanate 151.4 parts, 2,2-dimethylol propionic acid 36.3 parts, methyl ethyl ketone 550 parts, under 80 DEG C of conditions, carry out ammonia esterification 10 hours, obtain the urethane prepolymer 1100 parts of isocyanate group end.Next, this prepolymer is added drop-wise in the chain extender solution (triethylamine 24.6 parts, Virahol 41.1 parts, isophorone diamine 3.6 parts, adipic dihydrazide 12.1 parts, methyl ethyl ketone 434.9 parts) being in whipped state, mixing total overall reaction system.Afterwards, 60 DEG C of Keep agitation reaction systems 2 hours, chain is reacted and terminates, obtain that Tg is-10 DEG C, the aqueous solution (NV is 35 % by weight) of CA to be 0.5mmol/g, Mw the be urethane resin (PU-1) of 14000.
The preparation > of < silane coupling agent
Embodiment 1
By (A-1) composition 5 parts, tetramethylol methane-three-(β-aziridinyl propionic ester) (the content 7mmol/g of goods name " TAZO ", pharmaceutical worker's (strain) manufacture mutually, aziridinyl) (hereinafter referred to as TAZO) 1.2 parts, tosic acid (hereinafter referred to as PTS) 0.12 part, 28%NH
30.04 part, IPA8.4 part, IW8.4 part mixes in beaker, preparation NV is the silane coupling agent of 10 % by weight.
Embodiment 2 ~ 15, comparative example 1 ~ 43
Except using the raw material of number as shown in each table, by the method identical with embodiment 1, prepare silane coupling agent.
[table 2]
[table 3]
PZ-33: trimethylolpropane tris (β-aziridinyl propionic ester) (the content 7mmol/g of goods name " ケ ミ タ イ ト PZ-33 ", (strain) Japanese catalyst manufacture, aziridinyl)
SV-02: carbodiimide system solidifying agent (the content 2.3mmol/g of trade(brand)name " CarbodiliteSV-02 ", Nisshinbo chemical (strain) manufacture, carbodiimide)
WS-700: oxazoline system solidifying agent (the content 4.5mmol/g of trade(brand)name " EPOCROSWS-700 ", (strain) Japanese catalyst, oxazolinyl)
EX-612: epoxy solidifying agent (the content 5.9mmol/g of trade(brand)name " DENACOL ", NagasechemteX (strain) manufacture, epoxy group(ing))
(A)/(B): [usage quantity (g) (being converted into nonvolatile component) of content (mmol/g) × (A) composition of carboxylate anion's group of (A) composition]/[usage quantity (g) (being converted into nonvolatile component) of content (mmol/g) × (B) composition of the aziridinyl of (B) composition]
The preparation of < aluminium-vapour deposition plastic film and evaluation >
Use bar coater to the silane coupling agent of gained in commercially available PET film (goods name " E5100 ", Japan's weaving (strain) manufacture, 38 μm thick) coating Examples 1, making it dry film thickness is 1 μm, then by coated film dry (150 DEG C, 60 seconds) in recirculating air drying machine.
Next, be arranged on by the desciccator diaphragm of gained on commercially available evaporation coating device (goods name " NS-1875-Z ", Western Hills make institute's (strain) and manufacture), the thickness obtaining evaporation layer is the aluminium-vapour deposition film of 50nm.This film is used as the experimental film of embodiment 1.For other embodiment and comparative example, operate equally, prepare experimental film.
(outward appearance)
According to the outward appearance in the evaporation face of the experimental film of standard visual assessment embodiment 1 below.Also same evaluation is carried out to the experimental film of other embodiments and comparative example.Result is as shown in table 4 and table 5.
3 ... evaporation face does not produce albefaction
2 ... whole evaporation face produces few albefaction
1 ... whole evaporation face produces serious albefaction and interference fringe
(adhesion)
On the evaporation face of the experimental film of embodiment 1, paste self adhesive tape (goods name " Cellotape ", meter Qi Bang (strain) manufacture), vertically peel off well.In addition, also same evaluation is carried out to the experimental film of other embodiment and comparative example.Because aluminium-vapour deposition film all can not be peeling in any case, be therefore 3 entirely in table 4 and table 5.
(whitening resistance)
In the recirculating air drying machine of 150 DEG C, the outward appearance in the evaporation face after 60 minutes is heated according to the experimental film of following standard visual assessment embodiment 1.Result is as shown in table 4 and table 5.
4 ... evaporation face does not produce albefaction and interference fringe
3 ... local, evaporation face produces albefaction, does not produce interference fringe
2 ... whole evaporation face produces few albefaction and interference fringe
1 ... whole evaporation face produces serious albefaction and interference fringe
(processibility)
In commercially available acrylic panels (goods name " comoglas ", the manufacture of (strain) Kuraray, 5cm × 5cm × 1mm) coating Examples 1, the silane coupling agent of gained makes it dry film thickness is 1 μm, by in recirculating air drying machine under 150 DEG C of conditions dry 60 seconds, for the preparation of the test panel of resist processing test.In addition, the silane coupling agent of other embodiments and comparative example makes test panel similarly respectively.
In addition, as the bending utensil of described test panel, prepare the utensil of aluminium sheet (15cm × 5cm × 1mm) from middle bending 60 ° of gained.
Next, above-mentioned bending utensil is taken out after heating in (250 DEG C) in recirculating air drying machine, above-mentioned test panel is pressed about 3 seconds from acrylic panels side by the curved edges of this utensil of the condition of high temperature, bending about 80 ° afterwards, then according to the state of the aluminium-vapour deposition layer of following standard visual assessment crooked position.In addition, also same evaluation is carried out to the test panel of other embodiment and comparative example.Result is as shown in table 4 and table 5.
6 ... metal evaporation position is without breakage and peel off, and without fuzzy and interference fringe, range estimation judges, outward appearance is better than 5.
5 ... metal evaporation position is without breakage and peel off, and without fuzzy and interference fringe
4 ... metal evaporation position is without breakage and peel off, and only has fuzzy on a small quantity, but without interference fringe
3 ... metal evaporation position is without breakage and peel off, and only has fuzzy and interference fringe on a small quantity
2 ... there is tiny breakage at metal evaporation position and peels off, and has serious fuzzy and interference fringe
1 ... there is larger breakage at metal evaporation position and peels off, and has serious fuzzy and interference fringe
It should be noted that, owing to using thick acrylic panels, primary coat face (layer) can be made along the bending direction excessive tensile of panel.Its result, aluminium-vapour deposition layer easily cracks.The test conditions of such harshness is the condition of the physical device for mold-in injection shaping.
[table 4]
[table 5]
Embodiment 16 ~ 20, comparative example 44 ~ 46
The preparation of < tin evaporation plastic film and evaluation >
Using coating machine, in described PET film, in coating Examples 1, the silane coupling agent of gained makes it dry film thickness is 1 μm, then by coated film dry (150 DEG C, 60 seconds) in wind circulation dryer.Next, utilize described evaporation coating device, obtain the tin vapor-deposited film that evaporation layer thickness is 50nm.For the silane coupling agent of embodiment 8,11,13,15 and comparative example 29,31,33, operation obtains tin vapor-deposited film too.Next, according to the method for above-mentioned test subject and benchmark, the smoothness of each film, adhesion, whitening resistance and processibility are evaluated.Result is shown in table 6.
[table 6]
Claims (10)
1. be with an inorganic thin film plastics silane coupling agent, the second-order transition temperature that it comprises (A) has carboxylate anion's group is that acrylic copolymer, (B) of-5 ~ 120 DEG C at least has the polyaziridine compound of 3 aziridinyls, (C) as the tosic acid of aziridinyl ring opening catalyst and the ammonia as tosic acid neutralizing agent.
2. silane coupling agent as claimed in claim 1, wherein, (A) composition is the multipolymer neutralization of other unsaturated monomer reaction (a1) α, beta-unsaturated carboxylic acid, (a2) (methyl) alkyl acrylate and/or styrenic and (a3) added as required.
3. silane coupling agent as claimed in claim 1 or 2, wherein, carboxylate anion's group of (A) composition is 0.5 ~ 8mmol/g.
4. silane coupling agent as claimed in claim 1 or 2, wherein, the weight-average molecular weight of (A) composition is 3000 ~ 100000.
5. silane coupling agent as claimed in claim 1 or 2, wherein, (B) composition represents with following general formula,
In formula, X
1represent hydrogen, the alkyl of carbonatoms 1 ~ 6 or the hydroxyalkyl of carbonatoms 1 ~ 3, R
1represent hydrogen or methyl, R
2and R
3represent the alkyl of hydrogen or carbonatoms 1 ~ 6 respectively.
6. silane coupling agent as claimed in claim 1 or 2, wherein, the content ratio of (A) composition and (B) composition, namely
[usage quantity of the content of carboxylate anion's group of described (A) composition × be converted into (A) composition of nonvolatile component]/[usage quantity of the content of the aziridinyl of (B) composition × be converted into (B) composition of nonvolatile component]
In the scope of 0.01 ~ 10, the unit of the described content of carboxylate anion's group and the content of aziridinyl is mmol/g, and the unit of the usage quantity of (A) composition and the usage quantity of (B) composition is g.
7. be with inorganic thin film plastics, it contain plastic basis material, layer that silane coupling agent according to any one of claim 1 ~ 6 is formed and the layer that is made up of inorganic thin film.
8. band inorganic thin film plastics as claimed in claim 7, wherein, plastic basis material is membranaceous.
9. one kind using the mould internal shaping decorating film of band inorganic thin film plastics according to claim 8 as component.
10. one kind using the insert part forming decorating film of band inorganic thin film plastics according to claim 8 as component.
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| JP2010-041532 | 2010-02-26 | ||
| JP2010041532 | 2010-02-26 |
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| CN103540217B (en) * | 2013-10-08 | 2016-06-01 | 雅图高新材料有限公司 | The double-component aqueous car paint of acrylate resin that a kind of aziridine is crosslinked and its preparation method |
| JP6154872B2 (en) * | 2014-12-27 | 2017-06-28 | 三菱ケミカル株式会社 | Laminated polyester film |
| JP6113209B2 (en) * | 2015-01-29 | 2017-04-12 | 三菱樹脂株式会社 | Adhesive film |
| TWI688480B (en) * | 2015-09-25 | 2020-03-21 | 日商東洋油墨Ｓｃ控股股份有限公司 | Decorative film, method for producing same, and decorated molded article |
| WO2018151089A1 (en) | 2017-02-14 | 2018-08-23 | 出光ユニテック株式会社 | Laminate, molded article, and method for producing molded article |
| JP2021116374A (en) | 2020-01-28 | 2021-08-10 | 荒川化学工業株式会社 | Undercoat agent, cured product, and laminate |
| JP2022139500A (en) | 2021-03-12 | 2022-09-26 | 荒川化学工業株式会社 | Undercoat agent, coating agent kit, cured product and laminate |
| JP7441356B1 (en) | 2023-04-13 | 2024-02-29 | Ｄｉｃグラフィックス株式会社 | Water-based ink and laminates |
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| DE3663369D1 (en) * | 1985-01-16 | 1989-06-22 | Du Pont | Improved two-layer process for applying antistatic compositions to polyester supports |
| JPH0699578B2 (en) * | 1988-08-15 | 1994-12-07 | 帝人株式会社 | Easy-adhesive polyester film |
| EP1866154A1 (en) * | 2005-03-24 | 2007-12-19 | 3M Innovative Properties Company | Metallized films and articles containing the same |
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| KR20110098665A (en) | 2011-09-01 |
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