CN104419316A - Uv-curable composition for hard-coat paining - Google Patents
Uv-curable composition for hard-coat paining Download PDFInfo
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- CN104419316A CN104419316A CN201410405861.8A CN201410405861A CN104419316A CN 104419316 A CN104419316 A CN 104419316A CN 201410405861 A CN201410405861 A CN 201410405861A CN 104419316 A CN104419316 A CN 104419316A
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- acrylate
- urethane acrylate
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60Q—ARRANGEMENT OF SIGNALLING OR LIGHTING DEVICES, THE MOUNTING OR SUPPORTING THEREOF OR CIRCUITS THEREFOR, FOR VEHICLES IN GENERAL
- B60Q1/00—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor
- B60Q1/02—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to illuminate the way ahead or to illuminate other areas of way or environments
- B60Q1/04—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to illuminate the way ahead or to illuminate other areas of way or environments the devices being headlights
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V5/00—Refractors for light sources
- F21V5/04—Refractors for light sources of lens shape
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21W—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO USES OR APPLICATIONS OF LIGHTING DEVICES OR SYSTEMS
- F21W2102/00—Exterior vehicle lighting devices for illuminating purposes
Abstract
The invention provides an UV-curable composition for hard-coat painting comprises at least six polymerization of functional groups of aliphatic polyurethane acrylate oligomer in 100 weight portions, (b) benzotriazole modified polyurethane acrylate oligomer weight 5 to 20 weight portions, (c) polycarbonate modified polyurethane acrylate oligomer weight 5 to 15 weight portions, (d) oxidation stable agent 0.01 wt copies to 2 weight and (E) photopolymerization initiation agent 1 weight portions to 10 weight portions.
Description
The reference explanation of Patents
All disclosures that Korean Patent Application No. is 10-2013-0099307 by present patent application request, the applying date is on August 21st, 2013, Receiving Office is the korean patent application in Korea S's special permission Room are incorporated in the application as with reference to content.
Technical field
The present invention relates to ultraviolet hardening hardcoat coatings composition.In more detail, be adapted to the plastic substrate surface of polycarbonate etc., even if be positioned over outdoor environment for a long time, also can prevent from turning yellow and there are outstanding reliability, sticking power, hardness, wear resistance and shock-resistance etc. and the ultraviolet hardening hardcoat coatings composition of car headlamp lens dura mater etc. can be applicable to.
Background technology
Car headlamp (headlight) irradiates the lamp in front to enable automobile drive safely at night.The glass that traditional car headlamp market uses transparency outstanding is as front lamp cover (cover).
But the front lamp cover poor durability of this glass material, weight are large and manufacturing expense is high.For optimizing material lightweight and the cost optimization for reducing manufacturing expense of automobile oil expense, the front lamp cover produced at present generally uses transparency and the outstanding polycarbonate material of moldability.
But the transparency and the shock-resistance that are generally applicable to the polycarbonate material of car headlamp lens are outstanding, but scratch resistance, weathering resistance and chemical resistant properties are poor.Therefore, in order to make up the deficiency of polycarbonate material and scratch resistance and weathering resistance, need to use weathering resistance and the outstanding coating composition of scratch resistance to carry out the dura mater coating process of application.
No. 10-0199908th, Korean Patent No discloses this scratch resistance for raising polycarbonate material and uses the example of multifunctional acrylic ester oligopolymer.But, if said composition long-term exposure or when being positioned over outdoor environment, because of string stress intermolecular in film, serious film cracking and flavescence can be there is, cause the problem such as cosmetic injury and adhibit quality reduction, variable color of film.
And, the benzotriazole modified aliphatic urethane acrylate oligomer being included in ultraviolet hardening hardcoat coatings composition sclerotic type coating composition is generated by the reaction between the benzotriazole of hydroxyl and isocyanic ester and acrylic compound, is be the weathering resistance of film, scale resistance and the composition used.But benzotriazole modified aliphatic urethane acrylate irradiates 3,500kJ/m in promotion weathering resistance evaluation (SAE J1960)
2there occurs film during energy to come off and metachromatism phenomenon.This is that coming off of the benzotriazole caused because of irradiation ultraviolet radiation is caused.
Summary of the invention
A viewpoint of the present invention relates to ultraviolet hardening hardcoat coatings composition, it is characterized in that, comprising: (A) comprises aliphatic urethane acrylate oligopolymer 100 weight part of the polymerizable functional group of more than 6, (B) benzotriazole modified urethane acrylate oligopolymer 5 weight part to 20 weight part, (C) polycarbonate modified urethane acrylate oligomer 5 weight part to 15 weight part, (D) oxidation stabilizer 0.01 weight part to 2 weight part and (E) Photoepolymerizationinitiater initiater 1 weight part to 10 weight part.
In one concrete example, the aliphatic urethane acrylate oligopolymer that described (A) comprises the polymerizable functional group of more than 6 is: 2 functional aliphatic's isocyanate compounds and the resultant of reaction of hydroxy-acrylate monomer comprising more than 3 polymerizable unsaturated groups.
In one concrete example, the weight average molecular weight that described (A) comprises the aliphatic urethane acrylate oligopolymer of the polymerizable functional group of more than 6 is 1,000g/mol to 2,000g/mol.
In one concrete example, described (D) oxidation stabilizer comprises phenols and Phosphorus oxidation stabilizer with the ratio of 1:0.2 to 1:0.8 weight part.
In one concrete example, comprise aliphatic urethane acrylate oligopolymer 100 weight part of the polymerizable functional group of more than 6 relative to described (A), also comprise (F) polyfunctional acrylate monomer of 40 weight part to 70 weight parts.
In one concrete example, described (F) polyfunctional acrylate monomer comprises 2 functional acrylate's class monomers, more than one in 3 functional acrylate's class monomers and 6 functional acrylate's class monomers, described 2 functional acrylate's class monomers comprise butylene glycol diacrylate, 1,6-hexylene glycol acrylate, HDDMA, neopentylglycol diacrylate, propoxy-neopentylglycol diacrylate, Viscoat 335HP, tripropylene glycol diacrylate, more than one in TriMethylolPropane(TMP) dimethacrylate and polyethylene glycol acrylate (such as, Viscoat 335HP), described 3 functional acrylate's class monomers comprise propoxy-Viscoat 295, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, more than one in glycerol propoxylate triacrylate and tris isocyanurate triacrylate, and described 6 functional acrylate's class monomers comprise dipentaerythritol acrylate, in acrylate and caprolactone modification dipentaerythritol acrylate more than one of two (tetramethylolmethane) six.
In one concrete example, described (F) polyfunctional acrylate monomer comprises described 2 functional acrylate's monomers and 3 functional acrylate's monomers with the ratio of the weight part of 1:1.5 to 1:4.
In one concrete example, comprise aliphatic urethane acrylate oligopolymer 100 weight part of the polymerizable functional group of more than 6 relative to described (A), also comprise (G) UV light absorber 5 weight part to 20 weight part and (H) photostabilizer 1 weight part to 10 weight part.
Another viewpoint of the present invention relates to the headlamp lens comprising ultraviolet hardening hardcoat coatings composition.In one concrete example, described headlamp lens comprise plastic substrate; And dura mater, be formed at the one side of described plastic substrate; Described dura mater comprises aforesaid ultraviolet hardening hardcoat coatings composition.
In one concrete example, the thickness of described dura mater is 5 μm to 25 μm.
In one concrete example, described plastic substrate comprises more than one in polymethylmethacrylate (PMMA), polyethylene terephthalate (PET), PEN (PEN), triacetyl cellulose (TAC), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyethersulfone (PES), polyvinyl alcohol (PVA) and polyvinyl chloride (PVC).
Accompanying drawing explanation
Fig. 1 (a) is the promotion weathering resistance evaluation result of the test piece to comparative example of the present invention, and Fig. 1 (b) is the photo of the promotion weathering resistance evaluation result presenting the test piece manufactured in embodiments of the invention.
Embodiment
Illustrate in process of the present invention, when be judged as to relevant public technology or formation illustrate likely can obscure technology main idea of the present invention time, omit its detailed description.Further, the function that term described later is considered in the present invention defines, can be different according to the intention of user, fortune user or convention.Therefore, the definition of these terms should based on the content of whole specification sheets.
A viewpoint of the present invention relates to ultraviolet hardening hardcoat coatings composition.Described ultraviolet hardening hardcoat coatings composition comprises: comprise (A) and comprise the aliphatic urethane acrylate oligopolymer of the polymerizable functional group of more than 6, (B) benzotriazole modified urethane acrylate oligopolymer, (C) polycarbonate modified urethane acrylate oligomer, (D) oxidation stabilizer and (E) Photoepolymerizationinitiater initiater.
In one concrete example, described ultraviolet hardening hardcoat coatings composition comprises: (A), relative to aliphatic urethane acrylate oligopolymer 100 weight part of polymerizable functional group comprising more than 6, comprises (B) benzotriazole modified urethane acrylate oligopolymer 5 weight part to 20 weight part, (C) polycarbonate modified urethane acrylate oligomer 5 weight part to 15 weight part, (D) oxidation stabilizer 0.01 weight part to 2 weight part and (E) Photoepolymerizationinitiater initiater 1 weight part to 10 weight part.When comprising with described scope, there is the outstanding effect preventing turning yellow, reliability, thermotolerance, weathering resistance and resistance to chemical reagents.
Below, the composition of described ultraviolet hardening hardcoat coatings composition is illustrated in greater detail.
(A) the aliphatic urethane acrylate oligopolymer of the polymerizable functional group of more than 6 is comprised
When the described polymerizable functional group's aliphatic urethane acrylate oligopolymer (A) comprising more than 6 forms dura mater, hardness, cracking and scratch resistance can be improved.
In one concrete example, can use general described in comprise the aliphatic urethane acrylate oligopolymer (A) of the polymerizable functional group of more than 6.Such as, can be 2 functional aliphatic's isocyanate compounds and the resultant of reaction of hydroxy-acrylate monomer comprising more than 3 polymerizable unsaturated groups.
In one concrete example, described 2 functional aliphatic's isocyanate compounds can comprise more than one in hexamethylene diisocyanate, dicyclohexyl methane diisocyanate and isophorone diisocyanate, and described hydroxy-acrylate monomer can comprise more than one in pentaerythritol triacrylate, Dipentaerythritol triacrylate.
In one concrete example, described in comprise the aliphatic urethane acrylate oligopolymer (A) of the polymerizable functional group of more than 6 weight average molecular weight can be 1,000g/mol to 2,000g/mol.Preferably, 1,500g/mol to 2,000g/mol.In described scope, in the forming process of the dura mater of described ultraviolet hardening hardcoat coatings composition, outstanding to the adhibit quality of headlamp substrate, ultraviolet hardening hardcoat coatings composition hardening and workability.
(B) benzotriazole modified urethane acrylate oligopolymer
In one concrete example, general benzotriazole modified urethane acrylate oligopolymer (B) can be used.Such as, there is the resultant of reaction of the benzotriazole modified urethane acrylate of aliphatic urethane acrylate oligopolymer and hydroxyl.
In one concrete example, described aliphatic urethane acrylate oligopolymer can be 2 officials can aliphatic urethane acrylate oligopolymer and each molecule contain the resultant of reaction of the hydroxy-acrylate monomer of less than 2 polymerizable unsaturated groups.
The compound of the aliphatic isocyanates of described 2 officials' energy can comprise more than one in hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate.
Described each molecule sees more than one that comprises in Hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methylacrylate, hydroxybutyl acrylate, coumarinyl acid esters and methacrylic acid hydroxyl butyl ester containing the hydroxy-acrylate monomer of less than 2 polymerizable unsaturated groups.
General described benzotriazole modified urethane acrylate can be used in the present invention.Such as, can operating weight molecular-weight average be 300g/mol's to 500g/mol.In described scope, transparency and usability outstanding.
In one concrete example, the weight average molecular weight of described benzotriazole modified urethane acrylate oligopolymer (B) can be 800g/mol to 1,500g/mol.In described scope, weathering resistance of the present invention and resistance to chemical reagents outstanding.
In one concrete example, relative to aliphatic urethane acrylate oligopolymer (A) 100 weight part of polymerizable functional group comprising described more than 6, comprise benzotriazole modified urethane acrylate oligopolymer (B) described in 5 weight part to 20 weight parts.If described benzotriazole modified urethane acrylate oligopolymer (B) is within 5 weight parts, weathering resistance of the present invention and chemical resistant properties can reduce, during more than 20 weight part, and the more difficult and weathering resistance of sclerosis of the present invention and prevent flavescence effect from can reduce.
Preferably, the described benzotriazole modified urethane acrylate oligopolymer (B) of 8 weight part to 18 weight parts can be comprised, such as 10 weight part to 15 weight parts.Such as, 5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 and 20 weight parts can be comprised.
(C) polycarbonate modified urethane acrylate oligomer
Described polycarbonate modified urethane acrylate oligomer (C) is to improve elasticity of the present invention, snappiness and adhibit quality.
In one concrete example, described polycarbonate modified urethane acrylate oligomer (C) can use the aliphatic isocyanates compound of polycarbonate diol, 2 officials' energy and each molecule to contain the resultant of reaction of the hydroxy-acrylate monomer of the unsaturated group of less than 2.
The compound of the aliphatic isocyanates of described 2 officials' energy can use more than one in hexamethylene diisocyanate, dicyclohexyl methane diisocyanate and isophorone diisocyanate.
Described hydroxy-acrylate monomer can use more than one in Hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methylacrylate, hydroxybutyl acrylate, coumarinyl acid esters and methacrylic acid hydroxyl butyl ester.
In one concrete example, the weight average molecular weight of described polycarbonate modified urethane acrylate oligomer (C) can be 1,000g/mol to 2,000g/mol.Preferably, 1,500g/mol to 2,000g/mol.In described scope, outstanding to the adhibit quality of headlamp substrate, hardening and workability in the dura mater forming process of described ultraviolet hardening hardcoat coatings composition.
In one concrete example, relative to described aliphatic urethane acrylate oligopolymer (A) 100 weight part comprising the polymerizable functional group of more than 6, comprise the described polycarbonate modified urethane acrylate oligomer (C) of 5 weight part to 15 weight parts.When described polycarbonate modified urethane acrylate oligomer (C) is within 5 weight parts, the sticking power of coatings formed according to the present invention can reduce and obscission occurs, during more than 15 weight part, weathering resistance of the present invention and transparency can reduce.Preferably, relative to aliphatic urethane acrylate oligopolymer (A) 100 weight part, comprise the described polycarbonate modified urethane acrylate oligomer (C) of 5 weight part to 12 weight parts.Such as, 7 weight part to 10 weight parts can be comprised.In concrete example, relative to aliphatic urethane acrylate oligopolymer (A) 100 weight part, the described polycarbonate modified urethane acrylate oligomer (C) of 5,6,7,8,9,10,11,12,13,14 and 15 weight parts can be comprised.In described scope, elasticity, snappiness and adhibit quality can be improved.
(D) oxidation stabilizer
Described oxidation stabilizer (D) can suppress the main cause of flavescence phenomenon and the generation of quinone compounds and improve the effect preventing from turning yellow.Oxidation stabilizer described in the present invention (D) can use more than one in phenols and Phosphorus oxidation stabilizer.
In one concrete example, described phenol system oxidation stabilizer can use 2,6-bis--four-butyl-4-methylphenol, octadecyl-3-(3,5-bis--t-butyl-4-hydroxyphenyl) propionic ester, two (3, two (4'-hydroxyl-3'-t-butylbenzene base) butyric acid of 3-) glycol ester and four pairs of (methylene radical-3-(3,5-bis--t-butyl-4-hydroxyphenyl) propionic ester) methane etc.Can mix separately or two or more and use, but to be not limited thereto.Described Phosphorus oxidation stabilizer can use triphenyl phosphite, triisodecyl phosphite ester, phenylbenzene-iso-octyl group-phosphorous acid ester, three (2,4-bis--t-butylbenzene base) phosphorous acid ester, three (nonyl phenyl) phosphorous acid esters and distearyl-tetramethylolmethane-diphosphites etc.Can mix separately or two or more and use, but to be not limited thereto.When using oxidation stabilizer (D) of described kind, of the present inventionly prevent flavescence excellent.
In one concrete example, mix described phenol system and Phosphorus oxidation stabilizer with the weight part of 1:0.2 to 1:0.8 and use.Such as, mix with the weight part of 1:0.3 to 1:0.7.Such as, the weight part mixing of 1:0.4 to 1:0.6.When using with the mixing of described content ratio, thermostability of the present invention and weathering resistance outstanding.
In one concrete example, relative to described aliphatic urethane acrylate oligopolymer (A) 100 weight part comprising the polymerizable functional group of more than 6, comprise the described oxidation stabilizer (D) of 0.01 weight part to 2 weight part.When described oxidation stabilizer (D) is within 0.01 weight part, cannot effectively suppresses the generation of quinone compounds and flavescence phenomenon occur, during more than 2 weight part, the phenomenon that described oxidation stabilizer departs from coatings of the present invention can occur.
Preferably, 0.1 weight part to 2 weight part is comprised.Such as, 0.1 weight part to 1 weight part.In concrete example, relative to described aliphatic urethane acrylate oligopolymer (A) 100 weight part comprising the polymerizable functional group of more than 6, comprise the described oxidation stabilizer (D) of 0.01,0.05,0.1,0.5,1,1.5 and 2 weight parts.When described oxidation stabilizer (D) is within 0.01 weight part, cannot effectively suppresses the generation of quinone compounds and flavescence phenomenon occur, during more than 2 weight part, the phenomenon that described oxidation stabilizer departs from coatings of the present invention can occur.
(E) Photoepolymerizationinitiater initiater
In a specific example of the present invention, comprise Photoepolymerizationinitiater initiater (E).Described Photoepolymerizationinitiater initiater (E) forms coatings to harden according to composition of the present invention.In one concrete example, described Photoepolymerizationinitiater initiater (E) can use 2-hydroxy-2-methyl-1-phenyl-propane-1-phenyl ketone, 1-hydroxyl ring phenyl ketone, benzophenone (benzophen ketone), 1-(4-isopropyl phenyl) 2-hydroxyl 2-methyl 1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl propane 1-ketone, α, α-diethoxy acetophenone, 2,2-diethoxy 1-Phenyl ethyl ketone and two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide etc.Can mix separately or two or more and use, but to be not limited thereto.
In one concrete example, relative to described aliphatic urethane acrylate oligopolymer (A) 100 weight part, comprise the described Photoepolymerizationinitiater initiater (E) of 1 weight part to 10 weight part.When described Photoepolymerizationinitiater initiater (E) is within 1 weight part, the hardening of composition of the present invention can reduce and adhibit quality and scratch resistance reduce, during more than 10 weight part, adhesivity because of the viscosity of coating between workability and plastic substrate described later can reduce, and gonorrhoea phenomenon may occur on coatings surface.Preferably, 2 weight part to 8 weight parts are comprised.Such as, 3 weight part to 6 weight parts are comprised.In concrete example, relative to aliphatic urethane acrylate oligopolymer (A) 100 weight part, the described Photoepolymerizationinitiater initiater (E) of 1,2,3,4,5,6,7,8,9 and 10 weight parts can be comprised.The generation of the gonorrhoea phenomenon that the adhesivity in described scope between the outstanding and plastic substrate described later of workability is outstanding, can prevent coatings surface.
In another concrete example of the present invention, described ultraviolet hardening hardcoat coatings composition also can comprise (F) polyfunctional acrylate monomer.
(F) polyfunctional acrylate's monomer
In another concrete example of the present invention, described polyfunctional acrylate's monomer (F) is to improve hardness of the present invention, scratch resistance and adhibit quality.
In the present invention, described polyfunctional acrylate's monomer (F) can comprise have 2 officials can, 3 officials can and the monomer etc. of 6 functional acrylate functional groups.Can mix separately or two or more and use, but to be not limited thereto.
In one concrete example, described 2 functional acrylate's class monomers can use butylene glycol diacrylate, 1,6-hexylene glycol acrylate, 1,6-hexanediol dimethacrylate, neopentylglycol diacrylate, propoxy-neopentylglycol diacrylate, Viscoat 335HP, tripropylene glycol diacrylate, TriMethylolPropane(TMP) dimethacrylate and polyethylene glycol acrylate (such as, Viscoat 335HP) etc.Can mix separately or two or more and use, but to be not limited thereto.
In one concrete example, described 3 functional acrylate's class monomers can use propoxy-Viscoat 295, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, glycerol propoxylate triacrylate and tris isocyanurate triacrylate etc.Can mix separately or two or more and use, but to be not limited thereto.
In one concrete example, described 6 functional acrylate's class monomers can use dipentaerythritol acrylate, two (tetramethylolmethane) six acrylate and caprolactone modification dipentaerythritol acrylate etc.Can mix separately or two or more and use, but to be not limited thereto.
In one concrete example, described 2 functional acrylate's monomers and 3 functional acrylate's monomers of the weight part of 1:1.5 to 1:4 can be comprised.Such as, the weight part of 1:1.6 to 1:3 can be comprised.Such as, the weight part of 1:1.8 to 1:2 can be comprised.In described blend range, the hardness of coatings of the present invention, scratch resistance and adhibit quality are outstanding.
In one concrete example, relative to described aliphatic urethane acrylate oligopolymer (A) 100 weight part comprising the polymerizable functional group of more than 6, comprise described polyfunctional acrylate's monomer (F) of 40 weight part to 70 weight parts.When comprising with described scope, the research of chaotic phenomenon of coatings of the present invention can be prevented and there is homogenizing and the adhibit quality of outstanding described coatings.Preferably, 45 weight part to 65 weight parts are comprised.Such as, 55 weight part to 65 weight parts are comprised.In concrete example, relative to aliphatic urethane acrylate oligopolymer (A) 100 weight part, described polyfunctional acrylate's monomer (F) of 40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59,60,61,62,63,64,65,66,67,68,69 and 70 weight parts can be comprised.When comprising with described scope, the research of chaotic phenomenon of coatings of the present invention can be prevented and there is homogenizing and the adhibit quality of outstanding described coatings.
(G) UV light absorber
In another concrete example of the present invention, also can comprise UV light absorber (G).Described UV light absorber (G) be weathering resistance in order to improve coatings of the present invention and substrate prevent flavescence effect.Described UV light absorber (G) can use triazine system UV light absorber.In one concrete example, described UV light absorber (G) can use 6-[two (2,4-3,5-dimethylphenyl)-1,3,5-triazine, 6-[two (2,4-3,5-dimethylphenyl)-1,3,5 triazines and three [2,4,6-[2-{4-(octyl group-2-methyl acetic acid) oxygen-2 hydroxy phenyl }]-1,3,5 triazines etc.Can mix separately or two or more and use, but to be not limited thereto.
In one concrete example, relative to described aliphatic urethane acrylate oligopolymer (A) 100 weight part, comprise UV light absorber (G) described in 5 ~ 20 weight parts.Weathering resistance of the present invention and prevent flavescence excellent in described scope.Preferably, 10 ~ 20 weight parts are comprised.Such as, 10 ~ 15 weight parts are comprised.In concrete example, relative to aliphatic urethane acrylate oligopolymer (A) 100 weight part, the described UV light absorber (G) of 5,6,7,8,9,10,11,12,13,14 and 15 weight parts can be comprised.In described scope, weathering resistance of the present invention and prevent flavescence excellent.
(H) photostabilizer
In another concrete example of the present invention, described photostabilizer (G) is to prevent surface imperfection of the present invention and increasing weathering resistance.Described photostabilizer (G) can use hindered amine system ultraviolet hardening hardcoat coatings composition stablizer (hindered amine light stabilizer, HALS).In one concrete example, described hindered amine system ultraviolet hardening hardcoat coatings composition stablizer can use 2, 2, 6, 6-tetramethyl--4-piperidyl stearate, 1, 2, 2, 6, 6-pentamethyl--4-piperidyl benzoic ether, N-(2, 2, 6, 6-tetramethyl--4-piperidyl) dodecylsuccinimide, 1-((3, 5-2 the 3rd butyl-4-hydroxyphenyl) propionyloxyethyl)-2, 2, 6, 6-tetramethyl--4-piperidyl-(3, 5-2 the 3rd butyl-4-hydroxyphenyl) propionic ester, two (2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) sebate, two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl)-2-butyl-2-(3, 5-2 the 3rd butyl-4-hydroxybenzyl) malonic ester, N, N'-two (2, 2, 6, 6-tetramethyl--4-piperidyl) hexanediamine, four (2, 2, 6, 6-tetramethyl--4-piperidyl) butane tetracarboxylic acid esters, four (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) butane tetracarboxylic acid esters and two (2, 2, 6, 6-tetramethyl--4-piperidyl) two (tridecyl) butane tetracarboxylic acid esters etc.Can mix separately or two or more and use, but to be not limited thereto.
In one concrete example, relative to described aliphatic urethane acrylate oligopolymer (A) 100 weight part, the described photostabilizer (G) of 1 weight part to 10 weight part can be comprised.In described scope, surface imperfection of the present invention can be prevented and there is outstanding weathering resistance and prevent flavescence effect.Preferably, 2 weight part to 8 weight parts are comprised.Such as, 3 weight part to 6 weight parts can be comprised.In concrete example, relative to described aliphatic urethane acrylate oligopolymer (A) 100 weight part, the described photostabilizer (G) of 1,2,3,4,5,6,7,8,9 and 10 weight parts can be comprised.Described scope can prevent surface imperfection of the present invention and has outstanding weathering resistance and prevent flavescence effect.
Further, in a specific example of the present invention, also a kind of solvent can be comprised, workability when dissolving aforesaid ingredients and be easy to adjusting viscosity, the smoothness that can improve coatings and film.Described solvent can use general.Such as, alcohol system, ketone system and acetic ester series solvent can be used.
In one concrete example, described alcohol series solvent can use methyl alcohol, ethanol, Virahol, 2-methyl cellosolve, cellosolvo, propylene glycol monomethyl ether and propylene glycol monomethylether acetate.Can mix separately or two or more and use, but to be not limited thereto.
In one concrete example, described ketone series solvent can use methyl ethyl ketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), metacetone and butyrone etc.Can mix separately or two or more and use, but to be not limited thereto.
In one concrete example, described acetic ester series solvent can use ethyl acetate, butylacetate etc.
In one concrete example, relative to described aliphatic urethane acrylate oligopolymer (A) 100 weight part, the described solvent of 180 weight part to 240 weight parts can be comprised.In described scope, the physical property of composition of the present invention can not be hindered and there is outstanding viscosity adjustment and workability.Preferably, 190 weight part to 220 weight parts can be comprised.Such as, 190 weight part to 210 weight parts can be comprised.In concrete example, relative to described aliphatic urethane acrylate oligopolymer (A) 100 weight part, the described solvent of 180,185,190,195,200,205,210,215,220,225,230,235 and 240 weight parts can be comprised.In described scope, the physical property of composition of the present invention can not be hindered and there is outstanding viscosity adjustment and workability.
In another concrete example of the present invention, described ultraviolet hardening hardcoat coatings composition sclerotic type hardcoat coatings composition, except described composition, also can comprise wetting agent, levelling agent and the defoamer etc. that usually add coating composition to.These compositions are the smoothness in order to the workability and film strengthening coating.
Another viewpoint of the present invention relates to the headlamp lens comprising described ultraviolet hardening hardcoat coatings composition sclerotic type hardcoat coatings composition.In one concrete example, comprising: described headlamp lens comprise plastic substrate; And dura mater, be formed at the one side of described plastic substrate; Described dura mater comprises aforesaid ultraviolet hardening hardcoat coatings composition and is formed.
Described plastic substrate can use more than one in polymethylmethacrylate (PMMA), polyethylene terephthalate (PET), PEN (PEN), triacetyl cellulose (TAC), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyethersulfone (PES), polyvinyl alcohol (PVA) and polyvinyl chloride (PVC).Preferably, polycarbonate can be used.When using the plastic substrate of described kind, and the adhibit quality between ultraviolet hardening hardcoat coatings composition of the present invention can be outstanding.
In one concrete example, described dura mater is coated on the one side sclerosis of described plastic substrate with the thickness of 5 μm to 25 μm and forms ultraviolet hardening hardcoat coatings composition.In described scope, with the adhibit quality on described plastic substrate surface is outstanding, physical property is outstanding and can prevent bad order.Preferably, formed with the thickness of 5 μm to 20 μm.Such as, formed with the thickness of 7 μm to 15 μm.In concrete example, described dura mater is formed with the thickness of 5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24 and 25 μm.In described scope, with the adhibit quality on described plastic substrate surface is outstanding, physical property is outstanding and can prevent bad order.
Further, the making method of ultraviolet hardening hardcoat coatings composition sclerotic type hardcoat coatings composition of the present invention can use general method.Such as, the aforesaid aliphatic urethane acrylate oligopolymer (A) comprising the polymerizable functional group of more than 6, benzotriazole modified urethane acrylate oligopolymer (B), polycarbonate modified urethane acrylate oligomer (C), oxidation stabilizer (D), Photoepolymerizationinitiater initiater (E), polyfunctional acrylate's monomer (F), UV light absorber (G) and photostabilizer (H), solvent and surface modulation additive etc. put into dissolver, the mixing equipment such as stirrer, the general method of mixing within the scope of normal temperature is adopted to make.
Coating and sclerosis as described in the method for ultraviolet hardening hardcoat coatings composition sclerotic type hardcoat coatings composition of the present invention of making without particular restriction.As the method for the described coating composition of coating, widely used brushing, spraying, dip coated or rotary coating etc. in association area can be used, but be not limited thereto.
Below, formation of the present invention and effect is illustrated in greater detail by the preferred embodiments of the present invention.But, following examples just in order to contribute to understanding of the present invention, ranges of the present invention is not limited to following examples.Person skilled in the art of the present invention can technically class release do not record here content, therefore the description thereof will be omitted.
embodiment
embodiment 1 ~ 4 and comparative example 1 ~ 4
With following table 1 be composition and content basis, made ultraviolet hardening hardcoat coatings composition.
(A) 6 functional aliphatic's urethane acrylate oligomer: employ the reactant of molecular weight about 1,600g/mol, isophorone diisocyanate and pentaerythritol triacrylate and the DM87A of double bond chemical company (Double bond chemical).
(B) benzotriazole modified aliphatic urethane acrylate oligomer: the RUVA-93 employing large tomb (Otsuka) company.
(C) polycarbonate modified aliphatic urethane acrylate: the UA5095 employing U.S.'s source business.
(D) with the weight part of 1:0.4, phenol system oxidation stabilizer (SONGNOX1076 of Songwon company) and Phosphorus oxidation stabilizer (SONGNOX1680 of Songwon company) is employed.
(E) Photoepolymerizationinitiater initiater: the CP-4 employing U.S.'s source business.
(F-1) 2 functional acrylate's monomers: employ 1,6-hexylene glycol acrylate.
(F-2) 3 functional acrylate's monomers: employ Viscoat 295.
(F-3) 6 functional acrylate's monomers: employ dipentaerythritol acrylate (DIPENTAERYTHRITOL HEXAACRYLATE, DPHA).
(G) UV light absorber: employ (hydrazine phenyl triazine, HPT).
(H) photostabilizer: employ UV HALS (Tinuvin152, CIBA company).
(I) solvent: employ Virahol.
[table 1]
Test example
The ultraviolet hardening hardcoat coatings composition made in described embodiment 1 ~ 4 and comparative example 1 ~ 4 is in clear polycarbonate test piece (name of an article: Sanyo 3022L3), after about 12 μm of (dry coating thickness benchmark) pneumatic sprayings, under the temperature condition of 80 DEG C, warm air drying about 300 seconds and after eliminating solvent, with 300mW/cm
2high voltage mercury lamp about 20cm in atmosphere position on, with 3,500mJ/cm
2energy carry out irradiating and making it harden and obtain hard coat test piece, carried out the evaluation of following project to it, its result is with outstanding: zero, common: △, bad: ×, based on this, be indicated in table 2.
(1) adhibit quality test: according to ASTMD3359, implements cross-cut tape test (cross cut tapetest) and evaluates.Specifically, utilize cutter to draw each 11 horizontal x erect the line at 1mm interval and make 100 hurdles, adhesive tape is respectively closely connected after the hard coat test piece of described embodiment and comparative example, to the bottom of the direction horizontal stretch adhesive tape of trier, measure the number on the hurdle that film drops and be indicated in lower list 2.
(2) pencil hardness test: according to ISO15184 and JIS K5600-5-4, during more than HB, be evaluated as hardness outstanding.
(3) cut-through resistance test: utilize steel wool (Steelwool) 0000 grade (grade), apply 500g power and after rub (rubbing) 10 times, confirm to be coated with membrane damage, when film is not impaired: zero, when film is slightly impaired: △, during film obvious impaired: X, based on this, is indicated in table 2.
(4) anti-moisture test: test temperature and relative humidity are 50 ± 2 DEG C, place under the condition of 98 ± 2% after 240 hours and take out, place and to observe after 1 hour and to evaluate film with or without obvious variable color, fade, swelling, cracking, gloss reduction etc., adhibit quality has without exception etc., there is not the obvious variable color of film, fade, swelling, cracking, the reduction of gloss, the reduction etc. of adhibit quality: zero, slightly there is the obvious variable color of film, fade, swelling, cracking, the reduction of gloss, and adhibit quality is when slightly reducing: △, the obvious variable color of film, fade, swelling, cracking, gloss obviously reduces and adhibit quality obviously reduces time: ×, based on this, be indicated in table 2.
(5) water tolerance test: test piece is impregnated into tap water (TAP WATER, test temperature 40 DEG C) in after 240 hours take out, place 1 hour under normal temperature eliminated the moisture on surface by air blast (AIR BLOW) after, then the obvious variable color with or without film is observed, fade, swelling, cracking, gloss reduction etc., evaluating adhibit quality has without exception, if there is not the obvious variable color of film, fade, swelling, cracking, gloss reduces and adhibit quality does not reduce: zero, slightly there is the obvious variable color of film, fade, swelling, cracking, the reduction of gloss, and adhibit quality is when slightly reducing: △, the obvious variable color of film, fade, swelling, cracking, gloss obviously reduces and adhibit quality obviously reduces time: ×, based on this, be indicated in table 2.
(6) thermal test: place under test temperature (80 ± 2 DEG C) condition after 300 hours and take out, ambient temperatare observes the obvious variable color with or without film after putting 1 hour, fade, swelling, cracking, gloss reduction etc., evaluating adhibit quality has without exception, if there is not the obvious variable color of film, fade, swelling, cracking, gloss reduces and adhibit quality does not reduce: zero, slightly there is the obvious variable color of film, fade, swelling, cracking, the reduction of gloss, and adhibit quality is when slightly reducing: △, the obvious variable color of film, fade, swelling, cracking, gloss obviously reduces and adhibit quality obviously reduces time: ×, based on this, be indicated in table 2.
(7) Test for anti-chemical performance: use glass cleaner respectively, after machine oil comes and goes 20 times with the strength of 3N, rub film surface and after the outward appearance that detects by an unaided eye, ambient temperatare puts 24 hours, observe the obvious variable color with or without film, fade, swelling, cracking, gloss reduction etc., evaluating adhibit quality has without exception, if there is not the obvious variable color of film, fade, swelling, cracking, gloss reduces and adhibit quality does not reduce: zero, slightly there is the obvious variable color of film, fade, swelling, cracking, the reduction of gloss, and adhibit quality is when slightly reducing: △, the obvious variable color of film, fade, swelling, cracking, gloss obviously reduces and adhibit quality obviously reduces time: ×, based on this, be indicated in table 2.
(8) cold-hot cycle (Cycle) test: to test piece, (to place at 80 ± 2 DEG C and to place 3h → ambient temperatare at 3h → ambient temperatare puts 1h →-40 DEG C and put 1h → 50 ± 2 DEG C, 7 ~ 15h under 95%RH) be once, after repeatedly carrying out 5 times, ambient temperatare puts 1 hour, observe the obvious variable color with or without film, fade, swelling, cracking, gloss reduction etc., evaluating adhibit quality has without exception, if there is not the obvious variable color of film, fade, swelling, cracking, gloss reduces and adhibit quality does not reduce: zero, slightly there is the obvious variable color of film, fade, swelling, cracking, the reduction of gloss, and adhibit quality is when slightly reducing: △, the obvious variable color of film, fade, swelling, cracking, gloss obviously reduces and adhibit quality obviously reduces time: ×, based on this, be indicated in table 2.
(9) promote atmospheric exposure test: with the condition of the following xenon arc lamp specified in SAEJ2527, irradiate after 5 test pieces simultaneously, judge film whether variable color with aberration (Δ E).If Δ E is less than 3.0, be exactly that variable color does not occur.Evaluate with or without fading, swelling, cracking, gloss reduction etc. and adhibit quality have without exception.
(imposing a condition of * xenon arc lamp: 2,500KJ ㎡ and 4,500KJ/ ㎡ [340nm], BLACK PNL temperature-(LIGHT) 38 ± 2 DEG C (DARK) irradiate 40 minutes (50 ± 5%RH), cycle-irradiation 60 minutes (50 ± 5%RH) do not irradiate 60 minutes (95 ± 5%RH, surface/time injection-SPRAY), irradiate illumination-0.55 ± 0.02W/ (㎡ nm) [340nm])
(10) chip resistance (Chipping) property test: utilize test lithotripter (GRAVELO METER:SAEJ400 specification product), with following condition, after the test of chip resistance (CHIPPING) property is carried out to test film, whether evaluate has the obvious cracking, flaw etc. of film and adhibit quality to have without exception, if ftracture, flaw and adhibit quality do not reduce: zero, ftracture, flaw and adhibit quality be when reducing: ×, based on this, be indicated in table 2.
(* chip resistance (Chipping) property test conditions: 1) shooting distance (Shooting Distance): 150mm; 2) angle (Shooting Angle) is shot: 45 °; 3) shooting pressure (Shooting Pressure): 3.0Kgf/cm
2; 4) probe temperature (Test Temperature) :-40 DEG C; 5) rubble: 50g (JIS Crushedgravel No7 stone, 2.5 ~ 5mm, 350 ~ 400))
[table 2]
Fig. 1 (a) is the promotion weathering resistance evaluation result of the test piece to comparative example of the present invention, and Fig. 1 (b) is the photo of the promotion weathering resistance evaluation result presenting the test piece made in embodiments of the invention.The result of comprehensive described Fig. 1 and described test example, relative to embodiment 1 ~ 4, in the composition not comprising embodiments of the invention 1 ~ 4 or the comparative example 1 ~ 4 not meeting component proportions, hardness, adhibit quality, chemical resistant properties, weathering resistance etc. decrease.
Be explained above embodiments of the invention but the present invention be not limited to described embodiment, can with different variform manufactures, the technical field of the invention have general knowledge people, in the scope not changing technological thought of the present invention or intrinsic propesties, the present invention can be implemented with other concrete forms.Therefore, above disclosed embodiment is not determinate but exemplary.
Claims (11)
1. a ultraviolet hardening hardcoat coatings composition, is characterized in that, comprising:
(A) comprise aliphatic urethane acrylate oligopolymer 100 weight part of the polymerizable functional group of more than 6,
(B) benzotriazole modified urethane acrylate oligopolymer 5 weight part to 20 weight part,
(C) polycarbonate modified urethane acrylate oligomer 5 weight part to 15 weight part,
(D) oxidation stabilizer 0.01 weight part to 2 weight part and
(E) Photoepolymerizationinitiater initiater 1 weight part to 10 weight part.
2. ultraviolet hardening hardcoat coatings composition according to claim 1, is characterized in that:
The aliphatic urethane acrylate oligopolymer that described (A) comprises the polymerizable functional group of more than 6 is: 2 functional aliphatic's isocyanate compounds and the resultant of reaction of hydroxy-acrylate monomer comprising more than 3 polymerizable unsaturated groups.
3. ultraviolet hardening hardcoat coatings composition according to claim 1, is characterized in that:
The weight average molecular weight that described (A) comprises the aliphatic urethane acrylate oligopolymer of the polymerizable functional group of more than 6 is 1,000g/mol to 2,000g/mol.
4. ultraviolet hardening hardcoat coatings composition according to claim 1, is characterized in that:
Described (D) oxidation stabilizer comprises phenols and Phosphorus oxidation stabilizer with the ratio of 1:0.2 to 1:0.8 weight part.
5. ultraviolet hardening hardcoat coatings composition according to claim 1, is characterized in that:
Comprise aliphatic urethane acrylate oligopolymer 100 weight part of the polymerizable functional group of more than 6 relative to described (A), also comprise (F) polyfunctional acrylate monomer of 40 weight part to 70 weight parts.
6. ultraviolet hardening hardcoat coatings composition according to claim 5, is characterized in that:
Described (F) polyfunctional acrylate monomer comprises more than one in 2 functional acrylate's class monomers, 3 functional acrylate's class monomers and 6 functional acrylate's class monomers;
Described 2 functional acrylate's class monomers comprise butylene glycol diacrylate, 1, more than one in 6-hexylene glycol acrylate, HDDMA, neopentylglycol diacrylate, propoxy-neopentylglycol diacrylate, Viscoat 335HP, tripropylene glycol diacrylate, TriMethylolPropane(TMP) dimethacrylate and polyethylene glycol acrylate;
Described 3 functional acrylate's class monomers comprise more than one in propoxy-Viscoat 295, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, glycerol propoxylate triacrylate and tris isocyanurate triacrylate;
Described 6 functional acrylate's class monomers comprise in acrylate and caprolactone modification dipentaerythritol acrylate more than one of dipentaerythritol acrylate, two (tetramethylolmethane) six.
7. ultraviolet hardening hardcoat coatings composition according to claim 6, is characterized in that:
Described (F) polyfunctional acrylate monomer comprises described 2 functional acrylate's monomers and 3 functional acrylate's monomers with the ratio of the weight part of 1:1.5 to 1:4.
8. ultraviolet hardening hardcoat coatings composition according to claim 1, is characterized in that:
Comprise aliphatic urethane acrylate oligopolymer 100 weight part of the polymerizable functional group of more than 6 relative to described (A), also comprise (G) UV light absorber 5 weight part to 20 weight part and (H) photostabilizer 1 weight part to 10 weight part.
9. headlamp lens, comprising:
Plastic substrate; And
Dura mater, is formed at the one side of described plastic substrate;
Described dura mater comprises the ultraviolet hardening hardcoat coatings composition of any one in described claim 1 to 8.
10. headlamp lens according to claim 9, is characterized in that:
The thickness of described dura mater is 5 μm to 25 μm.
11. headlamp lens according to claim 9, is characterized in that:
Described plastic substrate comprises more than one in polymethylmethacrylate (PMMA), polyethylene terephthalate (PET), PEN (PEN), triacetyl cellulose (TAC), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyethersulfone (PES), polyvinyl alcohol (PVA) and polyvinyl chloride (PVC).
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