HK1116821A - Curable acrylate compositions, methods of making the compositions and articles made therefrom - Google Patents
Curable acrylate compositions, methods of making the compositions and articles made therefrom Download PDFInfo
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Description
Background
The present invention relates to curable acrylate coating compositions. More particularly, the present invention relates to curable acrylate coating compositions, methods of making the compositions, and articles made using the compositions.
The brightness enhancement films of the prior art typically include a high refractive index coating on a polyester film. The polyester-based brightness enhancement film does not have as high a luminosity (luminosity) as the polycarbonate-based film, possibly due to the inherent haze of the polyester. In addition, these brightness enhancement films for optical displays must pass battery tests to ensure long-term performance. In one of these tests, the brightness enhancement film (which includes a coating formulation containing phenylthioethyl acrylate) on polycarbonate film produced unacceptable amounts of haze and loss of luminosity during heat aging at 85 ℃ for 100 hours.
Thus, there is a need to provide coating compositions that maintain their optical brightness, i.e., do not produce excessive haze, especially in applications where brightness of the article is an important consideration.
Brief description of the invention
The present invention provides curable acrylate coating compositions. The composition comprises:
(a) a phenylthioethyl acrylate having formula I:
formula I
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12Cycloaliphatic radical, R2Is C1-C10An aliphatic group, n has a value of 0 to 5, wherein phenylthioethyl acrylate having formula I (hereinafter sometimes referred to as PTEA) comprises less than about 400 parts per million (hereinafter sometimes referred to as ppm) tin and less than about 2 wt% of the corresponding phenylthioethanol having formula II (hereinafter sometimes referred to as PTE):
formula II
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12A cycloaliphatic group, n has a value of from 0 to 5;
(b) at least one multifunctional (meth) acrylate; and
(c) at least one curing agent.
In additional embodiments, the curable acrylate coating composition further comprises at least one unsaturated acid. The unsaturated acid may be present in an amount corresponding to about 0.1 wt% to 1.0 wt%, based on the total weight of the curable acrylate coating composition.
In one other embodiment, the present invention provides a method of preparing a curable acrylate coating composition comprising:
blending components (a) - (d) to form a mixture, wherein
(a) Is PTEA having formula I comprising less than about 400ppm tin and less than about 2 wt% of the corresponding PTE having formula II;
(b) is at least one multifunctional (meth) acrylate; and
(c) is at least one curing agent; and
the mixture is heated to form a homogeneous composition.
In one embodiment, the present invention provides an article comprising a cured acrylate composition comprising structural units derived from:
PTEA having formula I, wherein the PTEA having formula I comprises less than about 400ppm tin and less than about 2 wt% of a corresponding PTE having formula II; and
at least one multifunctional (meth) acrylate.
In one aspect of the present invention, there is provided a curable coating composition comprising:
(a) PTEA having formula III:
formula III
Wherein the PTEA of formula III comprises less than about 400ppm tin and less than about 2 wt% of the corresponding PTE of formula IV; and
formula IV
At least one multifunctional (meth) acrylate; and
at least one curing agent.
In one embodiment, the present invention provides a cured acrylate coating composition comprising structural units derived from:
PTEA having formula I, wherein the PTEA having formula I comprises less than about 400ppm tin, the PTEA comprising less than about 2 wt% of a corresponding PTE having formula II; and
at least one multifunctional (meth) acrylate.
In one embodiment, the present invention provides an acrylate coating composition cured on a substrate comprising structural units derived from:
PTEA having formula I, wherein the PTEA having formula I comprises less than about 400ppm tin, the PTEA comprising less than about 2 wt% of a corresponding PTE having formula II; and
at least one multifunctional (meth) acrylate.
Brief Description of Drawings
FIG. 1 shows a custom coater made by Innovative Machine Corporation, Brirmingham, Alabama. The coater has a wound uncoated substrate film (10). The uncoated substrate film is unwound from a roll (web) (12) and passed between a nip roll (16) and a casting drum (18). The curable coating composition is applied as a coating bead (14) disposed between a nip roll (16) and a casting drum (18). The surface of the casting drum (18) is provided with a stencil (20) affixed to the outer surface, wherein the stencil includes a surface microstructure. The curable coating composition was cured using a high intensity UV lamp equipped with a V-bulb. The coated substrate film is then wound onto a roll (12) to provide a coated substrate film (24).
Fig. 2 shows an apparatus used for heat aging a coated substrate film (24). A coated substrate film comprising a substrate (10) and a cured acrylate coating containing microstructures (30) is covered with a polycarbonate film (28) and assembled in a glass jig (26).
Fig. 3-10 show the relationship between haze (34) and time in a coated substrate film (24) at 85 ℃ when a curable acrylate coating composition is used as the coating (32).
Detailed Description
The present invention will be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. In the following specification and the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings:
the singular forms "a" and "the" include plural referents unless the context clearly dictates otherwise.
"optional" and "optionally" means that the subsequently described event or circumstance may or may not occur, and that the term includes instances where the event occurs and instances where it does not.
The term "about" when used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the degree of error associated with measurement of the particular quantity).
The term "aliphatic radical" as used herein refers to a radical having valence states wherein at least one of the valence states consists of a linear or branched group of atoms which is not cyclic. The set of atoms may include heteroatoms such as nitrogen, sulfur, silicon, selenium and oxygen, or may be composed exclusively of carbon and hydrogen. Aliphatic groups may be substituted or unsubstituted. A substituted aliphatic group is defined as an aliphatic group that includes at least one substituent. Substituted aliphatic groups may include those available on aliphatic groups for removalAnd substituents in the same number of substitution positions. Substituents that may be present on an aliphatic group include, but are not limited to, halogen atoms, such as fluorine, chlorine, bromine, and iodine. Substituted aliphatic groups include trifluoromethyl, hexafluoroisopropylidene, chloromethyl, difluorovinylidene, trichloromethyl, bromoethyl, bromotrimethylene (e.g., -CH)2CHBrCH2-) and the like. For convenience, the term "unsubstituted aliphatic radical" is defined herein to encompass a wide range of functional groups as part of the "acyclic, straight chain or branched chain set of carbon atoms" comprising the unsubstituted aliphatic radical. Examples of unsubstituted aliphatic groups include allyl, aminocarbonyl (i.e., -CONH)2) Carbonyl, dicyanoiyisopropylene (i.e., -CH)2C(CN)2CH2-) methyl (i.e., -CH3) Methylene group (i.e., -CH)2-), ethyl, ethylene, formyl, hexyl, hexamethylene, hydroxymethyl (i.e., -CH)2OH), mercaptomethyl (i.e., -CH)2SH), methylthio (i.e., SCH)3) Methylthiomethyl (i.e., -CH)2SCH3) Methoxy, methoxycarbonyl, nitromethyl (i.e., -CH)2NO2) Thiocarbonyl, trimethylsilyl, t-butyldimethylsilyl, trimethoxysilylpropyl, vinyl, vinylidene and the like. An aliphatic radical is defined as comprising at least one carbon atom. C1-C10Aliphatic groups include substituted aliphatic groups and unsubstituted aliphatic groups containing at least one, but no more than 10, carbon atoms.
The term "aromatic radical" as used herein refers to a group of atoms having valence states at least one of which comprises at least one aromatic group. A set of atoms, at least one valence of which includes at least one aromatic group, may include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen. The term "aromatic radical" as used herein, is not limited to, phenyl, pyridyl, furyl, thienyl, naphthyl, phenylene, and biphenyl radicals. As mentioned, an aromatic group (radial) contains at least one aromatic group (group). Aromatic radicals always having 4n +2 "A delocalized "ring structure of electrons, wherein n is an integer equal to or greater than 1, can be exemplified by phenyl (n ═ 1), thienyl (n ═ 1), furyl (n ═ 1), naphthyl (n ═ 2), oxazolyl (azulenyl) (n ═ 2), anthracenyl (n ═ 3), and the like. The aromatic group may also include non-aromatic components. For example, a benzyl group is an aromatic radical containing a phenyl ring (the aromatic group) and a methylene group (the nonaromatic component). Similarly, the tetrahydronaphthyl radical is fused to the nonaromatic component- (CH)2)4Aromatic group on (C)6H3) Aryl group of (1). The aromatic group may be substituted or unsubstituted. A substituted aromatic radical is defined as an aromatic radical containing at least one substituent. A substituted aromatic group may include as many substituents as there are positions available on the aromatic group for substitution. Substituents that may be present on an aromatic group include, but are not limited to, halogen atoms, such as fluorine, chlorine, bromine, and iodine. Substituted aromatic groups include trifluoromethylphenyl, hexafluoroisopropylidene bis (4-phenoxy) (i.e., -OPhC (CF)3)2PhO-), chloromethylphenyl, 3-trifluorovinyl-2-thienyl, 3-trichloromethylphenyl (i.e., 3-CCl)3PPh), bromopropylphenyl (i.e., BrCH)2CH2CH2Ph-) and the like. For convenience, the term "unsubstituted aromatic radical" is defined herein to encompass a wide range of functional groups as part of the "set of atoms in which at least one valence state includes at least one aromatic radical". Examples of unsubstituted aromatic groups include 4-allyloxyphenoxy, aminophenyl (i.e., H)2NPh-), aminocarbonylphenyl (i.e., NH)2COPh-), 4-benzoylphenyl, dicyanoiyisopropylenebis (4-phenoxy) (i.e., -OPhC (CN)2PhO-), 3-methylphenyl, methylenebis (4-phenoxy) (i.e., -OPhCH)2PhO-), ethylphenyl, phenylvinyl, 3-formyl-2-thienyl, 2-hexyl-5-furyl; hexamethylene-1, 6-bis (4-phenoxy) (i.e., -OPh (CH)2)6PhO-), 4-hydroxymethylphenyl (i.e., 4-HOCH)2Ph), 4-mercaptomethylphenyl (i.e., 4-HSCH)2Ph), 4-methylthiophenyl (i.e., 4-CH)3SPh), methoxyphenyl, methoxycarbonylphenoxy (e.g., methylsalicyl), nitromethylphenyl (i.e., -Ph)CH2NO2) Trimethylsilylphenyl, t-butyldimethylsilylphenyl, vinylphenyl, vinylenebis (phenyl), and the like. The term "C3-C10Aromatic groups "include substituted aromatic groups and unsubstituted aromatic groups containing at least 3 but no more than 10 carbon atoms. Aromatic radical 1-imidazolyl (C)3H2N2) Represents C3An aromatic group. Benzyl (C)7H8-) represents C7An aromatic group.
The term "cycloaliphatic radical" as used herein refers to a radical having at least one valence comprising a group of atoms which is cyclic but which is not aromatic. As defined herein, a "cycloaliphatic radical" is free of aromatic groups. A "cycloaliphatic radical" may comprise one or more noncyclic components. For example cyclohexylmethyl (C)6H11CH2-) is a cycloaliphatic radical which contains a cyclohexyl ring (the group of atoms which is cyclic but which is not an aromatic hydrocarbon) and a methylene group (the noncyclic component). The cycloaliphatic radical may include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen. The cycloaliphatic group may be substituted or unsubstituted. A substituted cycloaliphatic radical is defined as a cycloaliphatic radical which comprises at least one substituent. A substituted cycloaliphatic radical may comprise as many substituents as there are positions available on the cycloaliphatic radical for substitution. Substituents which may be present on a cycloaliphatic radical include, but are not limited to, halogen atoms such as fluorine, chlorine, bromine and iodine. Substituted cycloaliphatic radicals include trifluoromethylcyclohexyl, hexafluoroisopropylidene bis (4-cyclohexyloxy) (i.e., -OC6H10C(CF3)2C6H10O-), chloromethyl cyclohexyl, 3-trifluorovinyl-2-cyclopropyl, 3-trichloromethyl cyclohexyl (i.e., 3-CCl)3C6H10-), bromopropylcyclohexyl (i.e., BrCH2CH2CH2C6H10-) and the like. For convenience, the term "unsubstituted cycloaliphatic radical" is defined herein to encompass a wide range of functional groups. Examples of cycloaliphatic radicals include 4-allyloxycyclohexyl, aminocyclohexyl (i.e.,H2NC6H10-), aminocarbonyl cyclopentyl (i.e., NH)2COC5H8-), 4-acetoxycyclohexyl, dicyanoisopropylenebis (4-cyclohexyloxy) (i.e., -OC6H10C(CN)2C6H10O-), 3-methylcyclohexyl, methylenebis (4-cyclohexyloxy) (i.e., -OC)6H10CH2C6H10O-), ethylcyclobutyl, cyclopropylvinyl, 3-formyl-2-tetrahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl; hexamethylene-1, 6-bis (4-cyclohexyloxy) (i.e., -OC)6H10(CH2)6C6H10O-); 4-Hydroxymethylcyclohexyl (i.e., 4-HOCH)2C6H10-), 4-mercaptomethylcyclohexyl (i.e., 4-HSCH)2C6H10-), 4-methylthiocyclohexyl (i.e., 4-CH)3SC6H10-), 4-methoxycyclohexyl, 2-methoxycarbonylcyclohexyloxy (2-CH)3OCOC6H10O-), nitromethylcyclohexyl (i.e., NO)2CH2C6H10-), trimethylsilylcyclohexyl, tert-butyldimethylsilylcyclopentyl, 4-trimethoxysilylethylcyclohexyl (for example, (CH)3O)3SiCH2CH2C6H10-), vinylcyclohexenyl, vinylidenebis (cyclohexyl), and the like. The term "C3-C10Cycloaliphatic radical "includes both substituted cycloaliphatic radicals and unsubstituted cycloaliphatic radicals containing at least three but no more than 10 carbon atoms. Cycloaliphatic radical 2-tetrahydrofuranyl (C)4H7O-) represents C4A cycloaliphatic group. Cyclohexylmethyl (C)6H11CH2-) represents C7A cycloaliphatic group.
As noted, the present invention relates generally to curable acrylate coating compositions. It has been found that the curable acrylate coating compositions of the present invention have a reduced tendency to form haze in articles containing the compositions. It has been found that the use of PTEA of formula I (which includes less than about 400ppm tin and less than about 2 wt% of the corresponding PTE having formula II) results in a significant reduction in the formation of haze in articles prepared from the curable acrylate coating composition. It has also been found that the incorporation of unsaturated acids in the composition in an amount equivalent to about 0.1 wt% to about 1.0 wt%, based on the total weight of the curable acrylate coating composition, results in a significant reduction in haze formation in articles containing the cured acrylate coating composition. The curable acrylate coating composition of the present invention will be obtained by blending PTEA having formula I (which includes less than about 400ppm tin and less than about 2 wt% of the corresponding PTE having formula II), at least one multifunctional (meth) acrylate, and at least one curing agent.
The curable acrylate coating composition of the present invention includes PTEA represented by formula I:
formula I
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12Cycloaliphatic radical, R2Is C1-C10An aliphatic group, and n has a value of 0 to 5, wherein the PTEA comprises less than about 400ppm tin and less than about 2 wt% of a corresponding PTE having formula II:
formula II
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12A cycloaliphatic group, and n has a value of from 0 to 5.
In one embodiment, PTEA is represented by formula III:
formula III
Wherein the PTEA comprises less than about 400ppm tin and less than about 2 wt% of corresponding PTE having formula IV,
formula IV.
In one embodiment of the invention, PTEA of formula I containing less than about 400ppm tin and less than about 2 wt% of the corresponding PTE having formula II is present in the curable acrylate coating composition in an amount equivalent to about 20 wt% to about 60 wt%, based on the total weight of the composition. In another embodiment, it is present in an amount equivalent to about 30 wt% to about 50 wt%, based on the total weight of the curable acrylate coating composition. In a preferred embodiment, PTEA of formula I, containing less than about 2 wt% of the corresponding PTE having formula II, is present in an amount equivalent to about 35 wt% to about 45 wt%.
The multifunctional (meth) acrylate used in the curable acrylate coating composition typically comprises at least one multifunctional (meth) acrylate of formula V:
formula V
Wherein R is3Is hydrogen or C1-C10An aliphatic group; x1Is O or S; r4Is selected from C1-C20Aliphatic radical, C3-C30Aromatic radical and C3-C20A cycloaliphatic group, and n is an integer having a value of from 2 to 4. In various embodiments, R4Groups such as alkylene and hydroxyalkylene disubstituted bisphenol a or bisphenol F ethers may be included, with the brominated forms of bisphenol a and bisphenol F being preferred. In a preferred embodiment, R4Having the formula VI:
formula VI
Wherein Q is-C (CH)3)2、-CH2-, -C (O) -, -S-, -S (O) -, or-S (O)2-; y is C1-C6An aliphatic group, b is an integer having a value of 1 to 10, m is an integer having a value of 0 to 4, and d is an integer having a value of 1 to 3.
Multifunctional (meth) acrylates may include monomers, dimer and trimer compounds produced by reacting acrylic or methacrylic acid with diepoxides. Typically, the diepoxide used is selected from bisphenol a diglycidyl ether; bisphenol F diglycidyl ether; tetrabromobisphenol a diglycidyl ether; tetrabromobisphenol F diglycidyl ether; 1, 3-bis- {4- [ 1-methyl-1- (4-oxiranylmethoxyphenyl) -ethyl ] phenoxy } -propan-2-ol; 1, 3-bis- {2, 6-dibromo-4- [1- (3, 5-dibromo-4-oxiranylmethoxyphenyl) -1-methylethyl ] phenoxy } -propan-2-ol; and the like; and combinations comprising at least one of the foregoing diepoxides.
Exemplary multifunctional (meth) acrylate compounds include 2, 2-bis (4- (2- (meth) acryloyloxyethoxy) phenyl) propane; 2, 2-bis ((4- (meth) acryloyloxy) phenyl) propane; acrylic acid 3- (4- {1- [4- (3-acryloyloxy-2-hydroxypropoxy) -3, 5-dibromophenyl ] -1-methylethyl }2, 6-dibromophenoxy) -2-hydroxy-propyl ester; acrylic acid 3- [4- (1- {4- [3- (4- {1- [4- (3-acryloyloxy-2-hydroxy-propoxy) -3, 5-dibromo-phenyl ] -1-methyl-ethyl } -2, 6-dibromo-phenoxy) -2-hydroxy-propoxy ] -3, 5-dibromo-phenyl } -1-methyl-ethyl) -2, 6-dibromo-phenoxy ] -2-hydroxy-propyl ester; and the like; and combinations comprising at least one of the foregoing multifunctional (meth) acrylates. In one embodiment, the multifunctional (meth) acrylate is based on the reaction product of tetrabrominated bisphenol A diglycidyl ether and acrylic acid, namely RDX51027, available from UCB Chemicals and represented by formula VII.
Formula VII
In one embodiment, the multifunctional (meth) acrylate is present in the curable acrylate coating composition in an amount corresponding to from about 25 to about 75 weight percent based on the total weight of the curable acrylate coating composition. In another embodiment, the multifunctional (meth) acrylate is present in an amount corresponding to about 30 to about 70 weight percent based on the total weight of the curable acrylate coating composition. In a preferred embodiment, the multifunctional (meth) acrylate is present in an amount corresponding to about 55 to about 65 weight percent based on the total weight of the curable acrylate coating composition.
In one embodiment, the curing agent used in the curable acrylate coating composition is at least one photoinitiator or at least one thermal initiator that will effectively promote polymerization of the curable acrylate coating composition when exposed to ultraviolet radiation or heat, respectively. Suitable materials for use as curing agents are disclosed in U.S. Pat. No.4576850, U.S. Pat. No.6848986, and in references such as Encyclopedia of Polymer technology. Examples of initiators include organic peroxides (e.g., benzoyl peroxide), azo compounds, quinones, nitroso compounds, acyl halides, hydrazones, mercapto compounds, pyridinium compounds, imidazoles, chlorotriazines, benzoin alkyl ethers, diketones, phenones (phenones), benzoin ethers, hydroxy and alkoxy alkylphenones, thioalkylphenylmorpholinyl alkyl ketones, acyl phosphine oxides, and mixtures thereof suitable commercially available examples of UV activated photoinitiating compounds are sold under the trade designations IRGACURE 651, IRGACURE 184, IRGACURE 369, and IRGACURE 819 (bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide), all of which are commercially available from Ciba Geigy Company, Lucirin TPO-L from BASFCorp, and DAROCUR 1173 from Merck & Co. Examples of suitable commercially available thermal initiators are sold under the trade designations VAZO 52, VAZO 64 and VAZO 67 azo compound thermal initiators, all of which are commercially available from e.i. dupont de nemours and co. An exemplary curing agent particularly useful in many instances is a material commercially available as a photoinitiator under the designation IRGACURE 819.
The curing agent is typically present in the curable acrylate coating composition in an amount corresponding to about 0.1 to about 3.0 weight percent, based on the total weight of the curable acrylate coating composition. In another embodiment, the curing agent is present in an amount corresponding to about 0.2 to about 1.0 weight percent based on the total weight of the curable acrylate coating composition. In a preferred embodiment, the curing agent is present in an amount equivalent to about 0.4 to about 0.6 weight percent based on the total weight of the curable acrylate coating composition.
In one embodiment, the curable acrylate coating composition further comprises at least one surfactant. The at least one surface active agent (surfactant) present in the curable acrylate coating composition of the present invention typically comprises a silicon-containing surfactant. In one embodiment, the silicon-containing surfactant used in the curable acrylate coating composition comprises dimethicone copolyol. It is believed that the surfactant assists in stripping the cured coating from the mold surface. Suitable surfactants include SILWETTML-77, a polyoxyalkylene modified polydimethylsiloxane surfactant, SILWETTML-720, a polyoxy ethyleneAlkyl modified polydimethylsiloxane surfactants, SILWETTML-7600, a polyoxyalkylene-modified polydimethylsiloxane surfactant, and SILWETTML-7602, a polyoxyalkylene modified polydimethylsiloxane surfactant, all of which are commercially available. In one embodiment, the surfactant used is SILWETTM L-7602。
The surfactant is typically present in the curable acrylate composition in an amount corresponding to about 0.05 to about 0.7 weight percent, based on the total weight of the composition. In another embodiment, the surfactant is present in an amount equivalent to about 0.1 to about 0.5 weight percent based on the total weight of the composition. In a preferred embodiment, the surfactant is present in an amount equivalent to about 0.2 to about 0.3 wt%.
In another embodiment, the present invention provides a curable acrylate composition further comprising an unsaturated acid. In one embodiment, the unsaturated acid comprises a compound of formula VIII:
of the formula VIII
Wherein R is5And R6Independently at each occurrence, selected from hydrogen, -C (O) -OH, C1-C6Aliphatic radical, C3-C20A cycloaliphatic radical and C2-C20An aromatic group. Suitable unsaturated carboxylic acids include acrylic acid, methacrylic acid, methylenemalonic acid, fumaric acid, phenylfumaric acid, phenylthiofumaric acid, maleic acid, and methylenesuccinic acid. In one embodiment, the acid used is selected from acrylic acid and methacrylic acid. In a preferred embodiment, the acid used is acrylic acid.
In embodiments of the present invention that include unsaturated acids, the unsaturated acids are typically present in an amount corresponding to about 0.1 to about 1.0 weight percent based on the total weight of the curable acrylic composition. In a preferred embodiment, the unsaturated acid is typically present in an amount corresponding to about 0.2 to about 0.5 weight percent based on the total weight of the curable acrylic composition.
The curable acrylate coating composition may optionally further comprise one or more additives selected from the group consisting of flame retardants, antioxidants, heat stabilizers, ultraviolet stabilizers, dyes, colorants, antistatic agents, and the like, and combinations comprising at least one of the foregoing additives, so long as they do not deleteriously affect the polymerization of the composition or its end use. The selection of particular additives and the amounts used thereof can be made by one skilled in the art without undue experimentation.
The curable propionate coating compositions of the invention can be prepared by blending the components for a period of time sufficient to produce a homogeneous composition with effective mixing and sufficient heating. The temperature at which the mixture forms a homogeneous composition determines the temperature to which the mixture can be heated without adversely affecting the components. For example, when blending UCB inc. rdxc51027 multifunctional (meth) acrylate (60 parts by weight (pbw)), PTEA of formula III containing 400ppm tin and 0.16 wt% PTE having formula IV, Ciba Specialty Chemicals IRGACURE 819 photoinitiator (0.50pbw), and GE Silicones SILWET7602 silicone copolymer (0.25pbw), the mixture will form a homogeneous composition when heated to 85 ℃ and stirred several times over a period of 30 minutes.
The present invention provides curable acrylate coating compositions, methods of making curable acrylate coating compositions, cured acrylate coating compositions prepared from the curable acrylate coating compositions, and articles containing the cured acrylate coating compositions, wherein the component PTEA having formula I in the curable acrylate coating composition comprises less than about 400ppm tin and less than about 2 wt% of the corresponding PTE having formula II. PTEA of formula I containing more than about 400ppm tin impurities can be purified by one or more caustic washes of the PTEA of formula I that will result in a dramatic drop in the amount of tin present and only a slight increase in the content of the corresponding PTE of formula II that may be present within the PTEA of formula I to be purified. It is believed that PTEA having formula I undergoes hydrolysis upon exposure to aqueous base. A reasonable choice of conditions used during the alkaline washing of PTEA having formula I will minimize hydrolysis of PTEA having formula I to the corresponding PTE having formula II and the corresponding (meth) acrylic acid, and the content of the corresponding PTE having formula II within the purified PTEA having formula I will not exceed 2 wt%. The base used is generally selected from aqueous solutions of sodium hydroxide, sodium carbonate, sodium bicarbonate and combinations of the foregoing. For example, a simple alkaline wash of PTEA of formula III containing 2350ppm of tin and 0.14 wt% of the corresponding PTE having formula IV at ambient temperature using a 5 wt% sodium bicarbonate solution will result in PTEA of formula III containing 400ppm of tin and 0.16 wt% of the corresponding PTE having formula IV.
The present invention also provides articles made using the cured acrylate coating compositions prepared from the curable acrylate coating compositions of the present invention. When forming articles from curable acrylate coating compositions, it is often preferred to remove air bubbles by applying vacuum or the like, under mild heat (if the mixture is viscous), and to cast or otherwise produce a film of the composition on the desired surface. Referring to fig. 1, in one embodiment, a radiation curable acrylate coating composition (14) is applied to the surface of an uncoated base film substrate (10). The composition (14) can be applied to a base film substrate (10), and the base film substrate with the uncured coating of composition can then be passed through a compression nip defined by a nip roll (16) and a casting drum (18), which can have a negative pattern master of microstructures (20). The casting drum (18) may be maintained at a slightly elevated temperature sufficient to ensure that the pattern of microstructures is imprinted onto the coated side of the uncured film surface. The compression nip applies sufficient pressure to the uncured composition (14) and the base film substrate (10) to control the thickness of the composition coating and to sufficiently double contact the extruded composition with both the base film substrate (10) and the casting drum (18) to exclude any air between the uncured composition (14) and the casting drum (18). The radiation curable composition is cured by directing radiation energy through the base film substrate from a surface opposite the surface having the composition coating while the composition is in sufficient contact with the drum to cause replication of the pattern of microstructures within the cured composition layer.
In one embodiment, the curable acrylate coating composition is cured by performing photocuring. In another embodiment, the photocuring is performed using ultraviolet (hereinafter UV) radiation, where the wavelength of the UV radiation corresponds to from 1800 angstroms to about 4000 angstroms. Lamp systems used to generate such radiation include ultraviolet lamps and discharge lamps, such as xenon, metal halides, metal arcs, low or high pressure mercury vapor discharge lamps, and the like. Photocuring refers to the simultaneous inclusion of polymerization and crosslinking processes to form a tack-free cured acrylate composition.
In one embodiment, the curable acrylate coating composition is cured by performing heat curing, thermal curing, or electron beam curing. In another embodiment, the temperature at which thermal curing is achieved, typically corresponds to about 80 ℃ to about 130 ℃. In a preferred embodiment, the temperature corresponds to about 90 ℃ to about 110 ℃. In another embodiment, electron beam curing is typically achieved at an electron beam dose in the range of about 10kGy (Kilogey) or to about 100 kGy. In preferred embodiments, the electron beam dose is less than about 50kGy or less, depending on the nature of the polymer and the amount of polyfunctional additive present, and the presence of polyfunctional additive will reduce the required dose. The presence of multifunctional additives can also place limits on the electron beam dose used. At a certain level a peak is reached, after which the increased level of high temperature shear will decrease, but still above the level that existed before curing. The curable acrylate coating composition may be electron beam cured using an electron beam system as described in US 5981963.
The period of time required to heat the curable acrylate coating composition to obtain a cured coating composition depends on the components in the curable acrylate coating composition. Typically, the time period is equivalent to about 30 seconds to about 24 hours. In another embodiment, the period of time corresponds to about 1 minute to about 10 hours. In a preferred embodiment, the period of time corresponds to about 2 minutes to about 5 hours. This curing can be done in stages to produce a partially cured and often tack-free composition, which is then sufficiently cured by heating for an extended period of time or temperature within the aforementioned ranges.
In one embodiment, the curable acrylate coating composition is both UV curable and thermally curable.
The haze values of articles prepared using the curable acrylate coating composition of the present invention were measured using the apparatus described in fig. 2. The apparatus consists of a glass holder (26), the glass holder (26) consisting of a substrate film (10) coated with a cured acrylate coating composition (30), the substrate film (10) comprising a surface microstructure (30), the surface microstructure (30) in turn being covered with a polycarbonate film (28), wherein the polycarbonate film (28) is in contact with the microstructured surface of the cured coated substrate film. The initial HAZE of the covered polycarbonate film was measured using a BYK-GARDNER HAZE-GARD PLUS apparatus according to the procedure set forth in ASTM D1003. The apparatus was then placed in an oven and the coated polycarbonate film was removed at regular intervals and measured to determine the haze formation described above.
In one embodiment, the present invention provides an article prepared from a curable acrylate coating composition. Articles that can be made from the composition include, for example, optical articles such as light control films, brightness enhancement films for use in invisible light displays; an optical lens; a Fresnel lens; an optical disc; diffuser films, holographic substrates; or in combination with conventional lenses, prisms or mirrors.
The articles of the invention are characterized by having replicated microstructures, such as projections and depressions, having a plurality of utilitarian discontinuities, wherein the surface can be readily peeled away after radiation curing, without loss of mold detail and retention of replication of such detail under various conditions during use.
The term "microstructure" is used herein as defined and described in U.S. Pat. No.4576850, the disclosure of which is incorporated herein by reference. Thus, it is meant that the surface texture that depicts or characterizes the intended desired utility purpose or function of the article has a microstructure. Discontinuities (e.g., protrusions and depressions) in the surface of the article are morphologically offset from the average centerline obtained by the microstructure such that the sum of the areas encompassed by the surface curves above the centerline is equal to the sum of the areas below the line, wherein the line is substantially parallel to the nominal surface (bearing the microstructure) of the article. The height of the deviation is typically about + -0.005 to + -750 microns as measured by a representative characteristic feature length of the surface, e.g., 1-30cm, using optical or electron microscopy. The average centerline may be piano-shaped, concave, convex, non-spherical, or a combination thereof. Articles in which the deviation is of low order, for example from 0.005 to 0.1, or preferably to 0.05 microns, and in which the deviation has a infrequent or minimal chance that the surface does not have any significant discontinuities, are those in which the surface bearing the microstructures is a substantially "flat" or "smooth" surface, and such articles may be used, for example, as precision optical elements or elements having a precision optical interface, such as spectacle lenses. Articles in which the deviation is of low order and with frequent chance include those with antireflective microstructures. Articles in which the deviation magnitude is high, for example from ± 0.1 to ± 750 microns, and which are due to microstructures containing multiple practical discontinuities which are the same or different and which are spaced apart or continuous in a random or ordered manner, are articles such as retroreflective cube-corner sheeting (cube-corner sheeting), linear fresnel lenses, optical audio-visual discs and LMFs. The microstructure-bearing surface may contain practical discontinuities of both the high and low orders of magnitude. The microstructure-bearing surface may comprise extraneous or non-utilitarian continuous dots so long as the number or type thereof does not significantly interfere with or adversely affect the intended desired efficacy of the article. Typically, it is necessary or desirable to select a specific oligomer composition whose shrinkage, once cured, does not result in such interfering extraneous discontinuities, for example a composition that shrinks only 2-6%, and this requirement can be met by the curable acrylate compositions of the present invention.
The articles have a wide variety of desirable properties, such as toughness, flexibility, optical clarity and uniformity, and are resistant to common solvents. The microstructure of such articles has high thermal dimensional stability, resistance to abrasion and impact, and in one embodiment, the refractive index of the article manufactured using the cured acrylate coating composition is at least 1.57, even when the article is bent to an angle as large as 180 degrees.
While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope and spirit of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. The invention is further illustrated by the following non-limiting examples.
Examples
The following examples are set forth to provide those of ordinary skill in the art with a detailed description of how the invention claimed herein is evaluated, and are not intended to limit the scope of what the inventors regard as their invention unless otherwise indicated, parts by weight and temperatures in units of ° c.
The haze value formed in the polycarbonate film shown in FIG. 2 was measured according to ASTM procedure D1003.
In embodiments, PTEA and PTE refer to PTEA having formula III and less than PTE having formula IV, respectively. The impurities included, i.e. the tin and PTE content in the PTEA, are given in the table below.
Experiment of
Comparative examples 1-5 illustrate the negative effect of residual PTE and residual tin catalyst on the performance of multilayer films prepared using compositions comprising PTEA containing PTE and tin impurities.
The curable acrylate coating composition of comparative example 1 was prepared by combining UCB Inc. RDX51027 epoxy acrylate (60 parts by weight (pbw)), PTEA (40pbw, containing 0.14 wt% PTE and 2350ppm tin), Ciba Specialty Chemicals IRGACURE 819 photoinitiator (0.50pbw) and GE Silicones SILWET7602 silicone copolymer (0.25 pbw). The mixture was heated to 85 ℃ and stirred several times over a period of 30 minutes to obtain a homogeneous solution.
Comparative examples 2-5 curable acrylate coating compositions were prepared in a manner similar to comparative example 1. Wherein additionally the compositions were blended with varying amounts of PTE, as shown in table 1 below.
The compositions provided in table 1 were then used separately in the preparation of multilayer films comprising polycarbonate substrate films and cured acrylate film layers comprising microreplicated structures. A multi-layer film was prepared using a special coater made by innovative machine Corporation, Birmingham, Alabama, as described in fig. 1.5 g of a curable acrylate coating composition prepared as described in comparative example 1 was applied as the coating bead (14) across the web (12) by placing the coating bead (14) between a nip roll (16) and a casting drum (18) and passing the uncoated substrate film between the nip roll (16) and the casting drum (18). The casting drum was maintained at 50 ℃. The casting drum is provided with a stencil (20) affixed to an outer surface thereof, the stencil including a surface microstructure. The curable acrylate coating composition is cured using a high intensity lamp (20) equipped with a V-bulb. The spool (12) was operated at 50 feet/minute.
The heat aging of the multilayer film prepared as described above was performed in the following manner. Each film was assembled with a protective sheet of polycarbonate film (28) in a glass jig (26), as shown in fig. 2. The percent HAZE of each protective sheet of polycarbonate film (28) was measured prior to assembly of the film in this manner using a BYM-GARDNER HAZE-GARD PLUS apparatus according to the procedure set forth in ASTM D1003. A glass fixture comprising a polycarbonate film (28) and a substrate coated with a curable acrylate coating composition containing a microreplicated microstructure (24), in this case the polycarbonate film, is then placed in an oven maintained at about 85 ℃. At various time intervals, the apparatus was removed from the oven and the haze of the polycarbonate film (28) sheet was measured as described above.
The results of the heat aging test are set forth in table 1 below and fig. 3. The data of fig. 3 indicates that the presence of residual PTE and residual tin in the curable acrylate coating composition will result in the generation of haze in the polycarbonate film layer adjacent to the microreplicated film surface within the multilayer film, indicating that the adjacent polycarbonate film is sensitive to the presence of PTE and tin impurities originally present in the curable acrylate composition used. The formation of a haze of about 0.4% after 1000 hours at 85 ℃ is an indication of an undesirable haze level.
TABLE 1
| COMPARATIVE EXAMPLE (CE) | Corresponding curves in fig. 3 | Curable coating compositions prepared according to comparative examples 1-5 | Added amount ofOuter PTE (wt%) | Time (h) | Haze degree |
| CE-1 | 36 | 100 | 0 | 0 | 0.15 |
| 109 | 0.265 | ||||
| 205.5 | 0.344 | ||||
| 270.5 | 0.324 | ||||
| 357.5 | 0.411 | ||||
| 409 | 0.463 | ||||
| 567.5 | 0.527 | ||||
| 883 | 0.634 | ||||
| CE-2 | 38 | 99.9 | 0.1 | 0 | 0.15 |
| 109 | 0.265 | ||||
| 205.5 | 0.344 | ||||
| 270.5 | 0.446 | ||||
| 357.5 | 0.512 | ||||
| 409 | 0.573 | ||||
| 567.5 | 0.676 | ||||
| 883 | 0.868 | ||||
| CE-3 | 40 | 99.8 | 0.2 | 0 | 0.15 |
| 109 | 0.265 | ||||
| 205.5 | 0.462 | ||||
| 270.5 | 0.567 | ||||
| 357.5 | 0.717 |
| 409 | 0.821 | ||||
| 567.5 | 1.011 | ||||
| 883 | 1.202 | ||||
| CE-4 | 42 | 99.5 | 0.5 | 0 | 0.15 |
| 109 | 0.598 | ||||
| 205.5 | 1.143 | ||||
| 270.5 | 1.201 | ||||
| 357.5 | 1.422 | ||||
| 409 | 1.526 | ||||
| 567.5 | 1.630 | ||||
| 883 | 1.74 | ||||
| CE-5 | 44 | 99.0 | 1.0 | 0 | 0.15 |
| 109 | 0.987 | ||||
| 205.5 | 1.686 | ||||
| 270.5 | 1.871 | ||||
| 357.5 | 1.92 | ||||
| 409 | 1.853 | ||||
| 567.5 | 1.9444 | ||||
| 883 | 2.774 |
Examples 1-5 the same curable acrylate coating composition as described in comparative example 1 was used, except that the PTEA used was washed one or more times with an aqueous base before being mixed with the other components in the curable acrylate coating composition. Examples 1-5 illustrate that alkaline washing results in a dramatic drop in the concentration of tin present in PTEA and only a modest increase in PTE content. The increased concentration of PTE is thought to be due to alkaline-induced hydrolysis of PTEA. These examples demonstrate the positive effect of reducing tin impurity levels in purified PTEA on the performance of multilayer films prepared using it.
In example 1, 100ml of a 5% sodium bicarbonate solution was added to 1 liter of PTEA (which contained 2350ppm tin and 0.14% PTE) and the mixture was vigorously stirred for about 1 minute. The layers were allowed to separate into an aqueous layer and an organic layer. The organic layer containing PTEA was separated, slurried with 5g of magnesium sulfate per 100g of PTEA in the organic layer, and filtered. Analysis indicated that the alkali washed PTEA layer had 400ppm tin and 0.16% PTE. The purification process described above was used in examples 2-5 and the changes are shown in table 2.
The base washed PTEA of examples 1-5 was then used alone to prepare a curable acrylate coating composition. The curable acrylate coating compositions of examples 1-5 were prepared by combining UCB Inc. RDX51027 epoxy acrylate (60 parts by weight (pbw)), PTEA (40pbw, PTEA subjected to various base washes as described in Table 2), Ciba specialty Chemicals IRGACURE 819 photoinitiator (0.50pbw) and GE Silicones SILWET7602 silicone copolymer (0.25 pbw). The mixture was heated to 85 ℃ and stirred several times over a period of 30 minutes to obtain a homogeneous solution.
These curable acrylate coating compositions were then used alone in the preparation of multilayer films comprising a polycarbonate substrate film and a cured acrylate film layer containing microreplicated structures in a manner similar to that described for comparative example 1. In a similar manner to comparative example 1, heat aging of the multilayer films prepared using the curable acrylate coating compositions of examples 1-5 was performed.
TABLE 2
| Examples | Corresponding curves in fig. 4 | Alkali washed PTEA | Tin (ppm) | PTE(％) | Time (h) | Haze (%) |
| 1 | 48 | With 5% NaHCO3Washing 1 time PTEA | 400 | 0.16 | 0 | 0.15 |
| 168 | 0.20 | |||||
| 303 | 0.24 | |||||
| 578 | 0.27 | |||||
| 2 | NA | With 5% NaHCO32 washes of PTEA | 220 | 0.15 | 0 | 0.15 |
| 168 | 0.16 | |||||
| 303 | 0.20 | |||||
| 578 | 0.20 | |||||
| 3 | NA | With 5% NaHCO33 washes of PTEA | 18 | NA | 0 | 0.15 |
| 168 | 0.17 | |||||
| 303 | 0.19 | |||||
| 578 | 0.23 | |||||
| 4 | NA | With 5% NaHCO3Washing 3 times and using 5 | 15 | NA | 0 | 0.15 |
| 168 | 0.18 |
| % NaOH 1-time washing of PTEA | 303 | 0.24 | ||||
| 578 | 0.26 | |||||
| 5 | NA | With 5% NaHCO3PTEA washed 3 times and 2 times with 5% NaOH | ＜10 | 0.21 | 0 | 0.15 |
| 168 | 0.15 | |||||
| 303 | 0.18 | |||||
| 578 | 0.19 | |||||
| Comparative example 6 | 46 | PTEA-without alkaline washing | 2350 | 0.14 | 0 | 0.15 |
| 109 | 0.265 | |||||
| 205.5 | 0.344 | |||||
| 270.5 | 0.324 | |||||
| 357.5 | 0.411 | |||||
| 409 | 0.463 | |||||
| 567.5 | 0.527 | |||||
| 883 | 0.634 |
NA-is not available
In comparative example 6, a curable acrylate coating composition was prepared as described in comparative example 1 using the PTEA used in examples 1-5 (initially containing 2350ppm tin and 0.14% PTE prior to the base wash), but without the base wash. Using this curable acrylate coating composition, a multilayer film was then prepared, which was subjected to heat aging as described above. The resulting haze values of the multilayer film prepared using the composition of comparative example 6 were compared with the haze values obtained in example 1, as shown in table 2 above and fig. 4.
The results shown in fig. 4, which lists the haze values obtained from multilayer films prepared using the curable acrylate coating compositions of example 1 and comparative example 6, show less tendency to fog when multilayer films were prepared using curable acrylate coating compositions containing alkali washed PTEA.
Examples 6-9 the same curable acrylate coating composition as described in comparative example 1 was used, except that the PTEA used to prepare the curable acrylate composition was subjected to a single base wash and was also mixed with acrylic acid and/or PTE. The curable acrylate coating composition was then used alone to prepare a multilayer film and the film was heat aged as described above. Examples 6-9 show that when the curable acrylate coating composition used to prepare the film includes acrylic acid and PTEA in a single caustic wash, the performance of the multilayer film will be improved.
The curable acrylate coating composition of example 6 was prepared by combining UCB inc. rdx51027 epoxy acrylate (60 parts by weight (pbw)), PTEA (40pbw, prepared as in example 1) with a single base wash, Ciba Specialty chemicals irgacure 819 photoinitiator (0.50pbw) and GE Silicones SILWET7602 silicone copolymer (0.25 pbw). The mixture was heated to 85 ℃ and stirred several times over a period of 30 minutes to obtain a homogeneous solution.
The curable acrylate coating compositions of examples 7, 8 and 9 were prepared by adding the specific amounts of acrylic acid and/or PTE shown in table 3 below to the curable acrylate coating composition of example 6.
The results shown in the table below and in fig. 5 show that acrylic acid is effective in reducing the fogging tendency during heat aging even when higher levels of PTE, e.g., 1.5%, are present in the curable acrylate coating composition.
TABLE 3
| Examples | Corresponding curves in fig. 5 | One wash PTEA containing curable acrylate coating compositions | Acrylic acid (pbw) | PTE(pbw) | Time (h) | Haze degree |
| 6 | 50 | 100 | 0 | 0 | 0 | 0.15 |
| 198 | 0.15 | |||||
| 401 | 0.18 | |||||
| 695 | 0.21 | |||||
| 1028 | 0.28 | |||||
| 7 | 52 | 99.5 | 0.5 | 0 | 0 | 0.15 |
| 198 | 0.16 | |||||
| 401 | 0.21 | |||||
| 695 | 0.24 | |||||
| 1028 | 0.25 | |||||
| 0 | 0.15 | |||||
| 8 | 54 | 98.5 | 0 | 1.5 | 198 | 0.38 |
| 401 | 0.61 | |||||
| 695 | 0.73 | |||||
| 1028 | 0.79 |
| 0 | 0.15 | |||||
| 9 | 56 | 98 | 0.5 | 1.5 | 198 | 0.20 |
| 401 | 0.25 | |||||
| 695 | 0.29 | |||||
| 1028 | 0.303 |
Examples 10-12 the same curable acrylate coating composition as described in comparative example 1 was used, except that the PTEA used to prepare the curable acrylate coating composition was subjected to a single base wash and was also optionally blended with PTE. The curable acrylate coating composition was then used alone to prepare a monolayer film and the film was heat aged as described above. Examples 10-12 show that cured acrylate coating compositions prepared using PTEA with one caustic wash improved the performance of multilayer films prepared using the compositions.
The curable acrylate coating composition of example 10 was prepared by combining UCB inc. rdx51027 epoxy acrylate (60 parts by weight (pbw)), PTEA (40pbw, prepared as in example 1) with a single caustic wash, Ciba Specialty chemicals irgacure 819 photoinitiator (0.50pbw) and gesilicon SILWET7602 silicone copolymer (0.25 pbw). The mixture was heated to 85 ℃ and stirred several times over a period of 30 minutes to obtain a homogeneous solution.
The curable acrylate coating compositions of examples 11 and 12 were prepared by adding specific amounts of PTE to the curable acrylate coating composition of example 10, as shown in table 4 below.
Using the curable acrylate coating compositions of examples 10-12, the multilayer film described in FIG. 2 was prepared and heat aged as described above.
The results shown in table 4 below and fig. 6 demonstrate that the use of base washed PTEA in preparing the curable acrylate coating composition renders the composition insensitive to trace amounts of PTE that may also be present in the curable acrylate coating composition.
TABLE 4
| Examples | Corresponding curves in fig. 6 | One wash PTEA (pbw) containing curable acrylate coating composition | PTE(pbw) | Time (h) | Haze (%) |
| 10 | 58 | 100 | 0 | 0 | 0.15 |
| 168 | 0.20 | ||||
| 303 | 0.24 |
| 578 | 0.27 | ||||
| 11 | 60 | 99.5 | 0.5 | 0 | 0.15 |
| 168 | 0.23 | ||||
| 303 | 0.25 | ||||
| 578 | 0.27 | ||||
| 12 | 62 | 98.5 | 1.0 | 0 | 0.15 |
| 168 | 0.23 | ||||
| 303 | 0.25 | ||||
| 578 | 0.28 |
Examples 13 to 15: the same curable acrylate coating composition as described in comparative example 1 was used except that the PTEA used to prepare the curable acrylate coating composition was subjected to two base washes and optionally also blended with PTE. The curable acrylate coating composition was then used alone to prepare a multilayer film and the film was heat aged as described above. Examples 13-15 show that cured acrylate coating compositions prepared using two caustic washes of PTEA will improve the performance of multilayer films prepared using the compositions.
The curable acrylate coating composition of example 13 was prepared by combining UCB inc. rdx51027 epoxy acrylate (60 parts by weight (pbw)), two caustic washes of PTEA (40pbw, prepared as in example 2), Ciba Specialty chemicals irgacure 819 photoinitiator (0.50pbw) and GE Silicones SILWET7602 silicone copolymer (0.25 pbw). The mixture was heated to 85 ℃ and stirred several times over a period of 30 minutes to obtain a homogeneous solution.
The curable acrylate coating compositions of examples 14 and 15 were prepared by adding specific amounts of PTE to the curable acrylate coating composition of example 13, as shown in table 5 below.
Using the curable acrylate coating compositions of examples 13-15, the multilayer film described in FIG. 2 was prepared and heat aged as described above.
The results shown in table 5 below and fig. 7 indicate that the use of two base washes of PTEA in preparing a curable acrylate coating composition renders the composition insensitive to trace amounts of PTE that may also be present in the curable acrylate coating composition.
TABLE 5
| Examples | Corresponding curves in fig. 7 | Two wash PTEA (pbw) containing curable acrylate coating composition | PTE(pbw) | Time (h) | Haze (%) |
| Article (A) | |||||
| 13 | 64 | 100 | 0 | 0 | 0.15 |
| 168 | 0.16 | ||||
| 303 | 0.20 | ||||
| 578 | 0.20 | ||||
| 14 | 66 | 99.5 | 0.5 | 0 | 0.15 |
| 168 | 0.22 | ||||
| 303 | 0.23 | ||||
| 578 | 0.25 | ||||
| 15 | 68 | 98.5 | 1.0 | 0 | 0.15 |
| 168 | 0.23 | ||||
| 303 | 0.26 | ||||
| 578 | 0.27 |
Examples 16 to 18: the same curable acrylate coating composition as described in comparative example 1 was used except that the PTEA used to prepare the curable acrylate coating composition was subjected to three base washes and optionally also blended with PTE. The curable acrylate coating composition was then used alone to prepare a monolayer film and the film was heat aged as described above. Examples 16-18 show that cured acrylate coating compositions prepared using PTEA with three caustic washes will improve the performance of multilayer films prepared using the compositions.
The curable acrylate coating composition of example 16 was prepared by combining UCB inc. rdx51027 epoxy acrylate (60 parts by weight (pbw)), PTEA (40pbw, prepared as in example 3) with three base washes, Ciba Specialty chemicals irgacure 819 photoinitiator (0.50pbw) and GE Silicones SILWET7602 silicone copolymer (0.25 pbw). The mixture was heated to 85 ℃ and stirred several times over a period of 30 minutes to obtain a homogeneous solution.
The curable acrylate coating compositions of examples 17 and 18 were prepared by adding the specified amounts of PTE to the curable acrylate coating composition of example 16, as shown in table 6 below.
Using the curable acrylate coating compositions of examples 16-18, the multilayer film described in FIG. 2 was prepared and heat aged as described above.
The results shown in table 6 below and fig. 8 demonstrate that the use of three base washes of PTEA in preparing a curable acrylate coating composition renders the composition insensitive to trace amounts of PTE that may also be present in the curable acrylate coating composition.
TABLE 6
| Examples | Corresponding curves in fig. 8 | Curable acrylate coating composition containing triple wash PTEA (pbw) | PTE(pbw) | Time (h) | Haze (%) |
| 16 | 70 | 100 | 0 | 0 | 0.15 |
| 168 | 0.17 | ||||
| 303 | 0.19 | ||||
| 578 | 0.23 | ||||
| 17 | 72 | 99.5 | 0.5 | 0 | 0.15 |
| 168 | 0.21 | ||||
| 303 | 0.28 | ||||
| 578 | 0.28 | ||||
| 18 | 74 | 98.5 | 1.0 | 0 | 0.15 |
| 168 | 0.24 | ||||
| 303 | 0.29 | ||||
| 578 | 0.29 |
Examples 19-21 use the same curable acrylate coating composition as described in comparative example 1, except that the PTEA used to prepare the curable acrylate coating composition was subjected to four base washes and was also optionally blended with PTE. The curable acrylate coating composition was then used alone to prepare a multilayer film and the film was heat aged as described above. Examples 19-21 show that cured acrylate coating compositions prepared using PTEA with four caustic washes will improve the performance of multilayer films prepared using the compositions.
The curable acrylate coating composition of example 19 was prepared by combining UCB inc. rdx51027 epoxy acrylate (60 parts by weight (pbw)), PTEA with four caustic washes (40pbw, prepared as in example 4), Ciba Specialty chemicals irgacure 819 photoinitiator (0.50pbw) and GE Silicones SILWET7602 silicone copolymer (0.25 pbw). The mixture was heated to 85 ℃ and stirred several times over a period of 30 minutes to obtain a homogeneous solution.
The curable acrylate coating compositions of examples 20 and 21 were prepared by adding the specified amounts of PTE to the curable acrylate coating composition of example 19, as shown in table 7 below.
Using the curable acrylate coating compositions of examples 19-21, the multilayer film described in FIG. 2 was prepared and heat aged as described above.
The results shown in table 7 below and fig. 9 demonstrate that the use of four base washes of PTEA in preparing a curable acrylate coating composition renders the composition insensitive to trace amounts of PTE that may also be present in the curable acrylate coating composition.
TABLE 7
| Examples | Corresponding curves in fig. 9 | Four wash PTEA (pbw) containing curable acrylate coating composition | PTE(pbw) | Time (h) | Haze (%) |
| 19 | 76 | 100 | 0 | 0 | 0.15 |
| 168 | 0.18 | ||||
| 303 | 0.24 | ||||
| 578 | 0.26 | ||||
| 20 | 78 | 99.5 | 0.5 | 0 | 0.15 |
| 168 | 0.23 | ||||
| 303 | 0.28 | ||||
| 578 | 0.29 | ||||
| 21 | 80 | 98.5 | 1.0 | 0 | 0.15 |
| 168 | 0.23 | ||||
| 303 | 0.27 | ||||
| 578 | 0.29 |
Examples 22-24 use the same curable acrylate coating composition as described in comparative example 1, except that the PTEA used to prepare the curable acrylate coating composition was subjected to five base washes and optionally also blended with PTE. The curable acrylate coating composition was then used alone to prepare a multilayer film and the film was heat aged as described above. Examples 22-24 show that cured acrylate coating compositions prepared using PTEA with five caustic washes will improve the performance of multilayer films prepared using the compositions.
The curable acrylate coating composition of example 22 was prepared by combining UCB inc. rdx51027 epoxy acrylate (60 parts by weight (pbw)), five base washes of PTEA (40pbw, prepared as in example 5), Ciba Specialty chemicals irgacure 819 photoinitiator (0.50pbw) and GE Silicones SILWET7602 silicone copolymer (0.25 pbw). The mixture was heated to 85 ℃ and stirred several times over a period of 30 minutes to obtain a homogeneous solution.
The curable acrylate coating compositions of examples 23 and 24 were prepared by adding the specified amounts of PTE to the curable acrylate coating composition of example 22, as shown in table 8 below.
Using the curable acrylate coating compositions of examples 22-24, the multilayer film described in FIG. 2 was prepared and heat aged as described above.
The results shown in table 8 below and fig. 10 demonstrate that the use of five base washes of PTEA in preparing a curable acrylate coating composition renders the composition insensitive to trace amounts of PTE that may also be present in the curable acrylate coating composition.
TABLE 8
| Examples | Corresponding curves in fig. 10 | Curable acrylate coating composition containing five washes of PTEA (pbw) | PTE(pbw) | Time (h) | Haze (%) |
| 22 | 82 | 100 | 0 | 0 | 0.15 |
| 168 | 0.15 | ||||
| 303 | 0.18 | ||||
| 578 | 0.19 | ||||
| 23 | 84 | 99.5 | 0.5 | 0 | 0.15 |
| 168 | 0.21 | ||||
| 303 | 0.22 | ||||
| 578 | 0.24 | ||||
| 24 | 86 | 98.5 | 1.0 | 0 | 0.15 |
| 168 | 0.22 | ||||
| 303 | 0.26 | ||||
| 578 | 0.27 |
Although the efficacy of the method of the present invention to control haze is demonstrated herein experimentally with haze control of UV curable acrylate coating compositions comprising unsubstituted PTEA comprising formula III, the present invention also includes haze control in articles made using compositions comprising a wide variety of substituted PTEA, wherein the compositions can be cured using heat or UV. Thus, while the following description and experimental details focus on haze control for articles made from unsubstituted PTEA, the present invention is in no way limited thereto. The present invention in its broadest sense includes haze control in articles made from any and all PTEA containing less than about 400ppm tin and less than about 2 wt% of the corresponding PTE.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood by those skilled in the art that various changes and modifications can be made within the spirit and scope of the invention.
Claims (24)
1. A composition, comprising:
a phenylthioethyl acrylate having formula I:
formula I
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12A cycloaliphatic group, n has a value of from 0 to 5, wherein said phenylthioethyl acrylate comprises less than about 400ppm tin, and said phenylthioethyl acrylate comprises less than about 2 wt% of a corresponding phenylthioethanol having the formula II:
formula II
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12A cycloaliphatic group, n has a value of from 0 to 5;
at least one multifunctional (meth) acrylate; and
at least one curing agent.
2. The composition of claim 1, further comprising at least one unsaturated acid, wherein the unsaturated acid is present in an amount corresponding to about 0.1 to about 1.0 weight percent based on the total weight of the composition.
3. The composition of claim 1, further comprising at least one surfactant.
4. The composition of claim 1, wherein the phenylthioethyl acrylate is of formula III:
formula III
Wherein the phenylthioethyl acrylate comprises less than about 400ppm tin and the phenylthioethyl acrylate comprises less than about 2 wt% of a corresponding phenylthioethanol having formula IV:
formula IV.
5. The composition of claim 1, wherein the multifunctional (meth) acrylate is represented by formula V:
formula V
Wherein R is3Is hydrogen or C1-C10An aliphatic group; x1Is O or S; r4Is selected from C1-C20Aliphatic radical, C3-C30Aromatic radical and C3-C20A cycloaliphatic group, and n is an integer having a value of 2 to 4.
6. The composition of claim 1, wherein the multifunctional (meth) acrylate is represented by formula VII:
formula VII.
7. The composition of claim 1, wherein the curing agent is selected from the group consisting of ultraviolet curing agents and thermal curing agents.
8. The composition of claim 3, wherein the surfactant is selected from the group consisting of silicon-containing surfactants.
9. The composition of claim 2, wherein the unsaturated acid has the formula VIII:
of the formula VIII
Wherein R is5And R6Independently at each occurrence, selected from hydrogen, -C (O) -OH, C1-C6Aliphatic radical, C3-C20A cycloaliphatic radical and C2-C20An aromatic group.
10. The composition of claim 2 wherein the unsaturated acid is selected from the group consisting of acrylic acid and methacrylic acid.
11. The composition of claim 1, wherein the phenylthioethyl acrylate is present in an amount corresponding to about 35 wt% to about 45 wt%, based on the total weight of the composition.
12. The composition of claim 1, wherein the multifunctional (methacrylate) is present in an amount corresponding to about 55 wt% to about 65 wt%, based on the total weight of the composition.
13. The composition of claim 2, wherein the unsaturated acid is present in an amount equivalent to 0.2 wt% to about 0.5 wt%, based on the total weight of the composition.
14. A method of making a composition, wherein the method comprises blending components (a) - (c) to form a mixture, wherein
(a) Is a phenylthioethyl acrylate having the formula I:
formula I
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12Cycloaliphatic radical, R2Is C1-C10Aliphatic seriesAnd n has a value of 0 to 5, wherein the phenylthioethyl acrylate comprises less than about 400ppm tin, and the phenylthioethyl acrylate comprises less than about 2 wt% of a corresponding phenylthioethanol having formula II:
formula II
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12A cycloaliphatic group, and n has a value of from 0 to 5;
(b) is at least one multifunctional (meth) acrylate; and
(c) is at least one curing agent; and
the mixture is heated to form a homogeneous composition.
15. An article comprising a cured acrylate composition comprising structural units derived from:
a phenylthioethyl acrylate having formula I:
formula I
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12Cycloaliphatic radical, R2Is C1-C10An aliphatic group, n has a value of 0 to 5, wherein said phenylthioethyl acrylate comprises less than about 400ppm tin, and said phenylthioethyl acrylate comprises less than about 2 wt% of a corresponding phenylthioethanol having formula II:
formula II
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12A cycloaliphatic group, n has a value of from 0 to 5; and
at least one multifunctional (meth) acrylate; and
at least one curing agent.
16. The article of claim 14 wherein said curing agent is a photoinitiator effective to promote polymerization.
17. The article of claim 14, wherein the article has a replicated microstructure on the coated film surface.
18. The article of claim 14, wherein the cured acrylate coating composition has a refractive index of at least 1.57.
19. A composition, comprising:
phenylthioethyl acrylate having formula III:
formula III
Wherein the phenylthioethyl acrylate comprises less than about 400ppm tin and the phenylthioethyl acrylate comprises less than about 2 wt% of a corresponding phenylthioethanol having formula IV:
at least one multifunctional (meth) acrylate; and
at least one curing agent.
20. The composition of claim 18, further comprising at least one unsaturated acid, wherein the unsaturated acid is present in an amount equivalent to about 0.1 wt% to about 1.0 wt%, based on the total weight of the composition.
21. A cured acrylate coating composition comprising structural units derived from:
a phenylthioethyl acrylate having formula I:
formula I
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12A cycloaliphatic group, n has a value of from 0 to 5, wherein said phenylthioethyl acrylate comprises less than about 400ppm tin, and said phenylthioethyl acrylate comprises less than about 2 wt% of a corresponding phenylthioethanol having the formula II:
formula II
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12A cycloaliphatic group, n has a value of from 0 to 5; and
at least one multifunctional (meth) acrylate.
22. A cured acrylate coating composition on a substrate, wherein the composition comprises structural units derived from:
a phenylthioethyl acrylate having formula I:
formula I
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12A cycloaliphatic group, n has a value of from 0 to 5, wherein said phenylthioethyl acrylate comprises less than about 400ppm tin, and said phenylthioethyl acrylate comprises less than about 2 wt% of a corresponding phenylthioethanol having the formula II:
formula II
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12A cycloaliphatic group, n has a value of from 0 to 5; and
at least one multifunctional (meth) acrylate.
23. A brightness enhancing film on a substrate, wherein the composition comprises structural units derived from:
a phenylthioethyl acrylate having formula I:
formula I
Wherein R is1Independently at each occurrence selected from C1-C10Aliphatic radical, C3-C20Aromatic radical and C3-C12A cycloaliphatic group, n has a value of 0 to 5, wherein said phenylthioethyl acrylate comprises less than about 400ppm tin, and said phenylthio acrylateThe ethyl-substituted ester comprises less than about 2 wt% of the corresponding phenylthioethanol having formula II.
24. The brightness enhancement film of claim 23 used in the manufacture of a display.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/074,272 | 2005-03-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| HK1116821A true HK1116821A (en) | 2009-01-02 |
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